Polymerisation catalysts

ABSTRACT

Catalyst systems useful for the polymerization of  1 -olefins are disclosed, which contain nitrogen-containing transition metal compounds comprising the skeletal unit depicted in Formula (B), wherein M is Fe[II], Fe[III], Ru[II], Ru[III] or Ru[IV]; X represents an atom or group covalently or ionically bonded to the transition metal M; T is the oxidation state of the transition metal M and b is the valency of the atom or group X; R 1 , R 2 , R 3 , R 4  and R 6  are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; R 5  and R 7  are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.

[0001] The present invention relates to transition metal-basedpolymerisation catalysts and to their use in the polymerisation andcopolymerisation of olefins.

[0002] The use of certain transition metal compounds to polymerise1-olefins, for example, ethylene, is well established in the prior art.The use of Ziegler-Natta catalysts, for example, those catalystsproduced by activating titanium halides with organometallic compoundssuch as triethylalumninium, is fundamental to many commercial processesfor manufacturing polyolefins. Over the last twenty or thirty years,advances in the technology have led to the development of Ziegler-Nattacatalysts which have such high activities that olefin polymers andcopolymers containing very low concentrations of residual catalyst canbe produced directly in commercial polymerisation processes. Thequantities of residual catalyst remaining in the produced polymer are sosmall as to render unnecessary their separation and removal for mostcommercial applications. Such processes can be operated by polymerisingthe monomers in the gas phase, or in solution or in suspension in aliquid hydrocarbon diluent. Polymerisation of the monomers can becarried out in the gas phase (the “gas phase process”), for example byfluidising under polymerisation conditions a bed comprising the targetpolyolefin powder and particles of the desired catalyst using afluidising gas stream comprising the gaseous monomer. In the so-called“solution process” the (co)polymerisation is conducted by introducingthe monomer into a solution or suspension of the catalyst in a liquidhydrocarbon diluent under conditions of temperature and pressure suchthat the produced polyolefin forms as a solution in the hydrocarbondiluent. In the “slurry process” the temperature, pressure and choice ofdiluent are such that the produced polymer forms as a suspension in theliquid hydrocarbon diluent. These processes are generally operated atrelatively low pressures (for example 10-50 bar) and low temperature(for example 50 to 150° C.).

[0003] Commodity polyethylenes are commercially produced in a variety ofdifferent types and grades. Homopolymerisation of ethylene withtransition metal based catalysts leads to the production of so-called“high density” grades of polyethylene. These polymers have relativelyhigh stiffness and are useful for making articles where inherentrigidity is required. Copolymerisation of ethylene with higher 1-olefins(eg butene, hexene or octene) is employed commercially to provide a widevariety of copolymers differing in density and in other importantphysical properties. Particularly important copolymers made bycopolymerising ethylene with higher 1-olefins using transition metalbased catalysts are the copolymers having a density in the range of 0.91to 0.93. These copolymers which are generally referred to in the art as“linear low density polyethylene” are in many respects similar to the socalled “low density” polyethylene produced by the high pressure freeradical catalysed polymerisation of ethylene. Such polymers andcopolymers are used extensively in the manufacture of flexible blownfilm.

[0004] In recent years the use of certain metallocene catalysts (forexample biscyclopentadienylzirconiumdichloride activated with alumoxane)has provided catalysts with potentially high activity. However,metallocene catalysts of this type suffer from a number ofdisadvantages, for example, high sensitivity to impurities when usedwith commercially available monomers, diluents and process gas streams,the need to use large quantities of expensive alumoxanes to achieve highactivity, and difficulties in putting the catalyst on to a suitablesupport.

[0005] Patent Application WO98/27124 published on Jun. 25, 1998discloses that ethylene may be polymerised by contacting it with certainiron or cobalt complexes of selected2,6-pyridinecarboxaldehydebis(imines) and 2,6-diacylpyridinebis(imines).

[0006] An object of the present invention is to provide a novel catalystsuitable for polymerising monomers, for example, olefins, and especiallyfor polymerising ethylene alone or for copolymerising ethylene withhigher I-olefins. A further object of the invention is to provide animproved process for the polymerisation of olefins, especially ofethylene alone or the copolymerisation of ethylene with higher 1-olefinsto provide homopolymers and copolymers having controllable molecularweights. For example, using the catalysts of the present invention therecan be made a wide variety of polyolefins such as, for example, liquidpolyolefins, oligomers, resinous or tacky polyolefins, solid polyolefinssuitable for making flexible film and solid polyolefins having highstiffness.

[0007] The present invention provides a polymerisation catalystcomprising

[0008] (1) a nitrogen-containing transition metal compound having thefollowing Formula B, and

[0009] (2) an activating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

[0010]  wherein M[T] is Fe[II], Fe[III], Co[I], Co[II], Co[III], Ru[II],Ru[III], Ru[IV], Mn[I], Mn[II], Mn[III] or Mn[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹, R², R³, R⁴, and R⁶ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and such that (1)

[0011]  when M is Fe, Co or Ru, R⁵ and R⁷ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and when any two ormore of R¹-R⁷ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents, or such that (2)

[0012]  when M is Fe, Co, Mn or Ru, then R⁵ is represented by the group“P” and R⁷ is represented by the group “Q” as follows:

[0013]  wherein R¹⁹ to R²⁸ are independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ andR¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbylor substituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents; with the proviso that at least one ofR¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl when neither of thering systems P and Q forms part of a polyaromatic fused-ring system, orsuch that (3)

[0014]  when M is Fe, Co, Mn or Ru, then R⁵ is a group having theformula —NR²⁹R³⁰ and R⁷ is a group having the formula —NR³¹R³², whereinR²⁹ to R³² are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and R²⁹ to R³²are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents.

[0015] Thus, one embodiment of the present invention provides apolymerisation catalyst comprising

[0016] (1) a nitrogen-containing transition metal compound comprisingthe skeletal unit depicted in Formula B and

[0017] (2) an activating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

[0018]  wherein M is Fe[II], Fe[III], Ru[II], Ru[III] or Ru[IV]; Xrepresents an atom or group covalently or ionically bonded to thetransition metal M; T is the oxidation state of the transition metal Mand b is the valency of the atom or group X; R¹, R², R³, R⁴ and R⁶ areindependently selected from hydrogen, halogen, hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; R⁵ andR⁷ are independently selected from hydrogen, halogen, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl.

[0019] When any two or more of R¹-R⁷ are hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, saidtwo or more can be linked to form one or more cyclic substituents.

[0020] A further embodiment of the present invention provides apolymerisation catalyst comprising

[0021] (1) a nitrogen-containing transition metal compound of Formula Zand

[0022] (2) an activating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

[0023]  wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I],Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents; with the proviso thatat least one of R¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl whenneither of the ring systems P and Q forms part of a polyaromaticfused-ring system. In this particular aspect of the present invention,in the case that neither of the ring systems P and Q forms part of apolyaromatic ring system, it is preferred that at least one of R¹⁹ andR²⁰, and at least one of R²¹ and R²² is selected from hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl. In one embodiment of the present invention, R¹⁹, R²⁰,R²¹ and R²² are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbylor substituted heterohydrocarbyl when neither of the ring systems P andQ forms part of a polyaromatic fused-ring system.

[0024] Subject to the foregoing provisos regarding R¹⁹, R²⁰, R²¹ and R²²in Formula Z, R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ in the compounds depicted inFormulae B and Z of the present invention are preferably independentlyselected from hydrogen and C₁ to C₈ hydrocarbyl, for example, methyl,ethyl, n-propyl, n-butyl, n-hexyl, and n-octyl. In Formula B, R⁵ and R⁷are preferably independently selected from substituted or unsubstitutedalicyclic, heterocyclic or aromatic groups, for example, phenyl,1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl,2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl,2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,3-dimethylphenyl,2,4-dimethylphenyl, 2-t-butylphenyl, 2,6-diphenylphenyl,2,4,6-trimethylphenyl, 2,6-trifluoromethylphenyl,4-bromo-2,6-dimethylphenyl, 3,5 dichloro2,6-diethylphenyl, and2,6,bis(2,6-dimethylphenyl)phenyl, cyclohexyl and pyridinyl.

[0025] The ring systems P and Q in Formula Z are preferablyindependently 2,6-hydrocarbylphenyl or fused-ring polyaromatic, forexample, 1-naphthyl, 2-naphthyl, 1-phenanthrenyl and 8-quinolinyl.

[0026] Another embodiment of the present invention provides apolymerisation catalyst comprising

[0027] (1) a nitrogen-containing transition metal compound of Formula Tand

[0028] (2) an activating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

[0029]  wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I],Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV], X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹ to R⁴, R⁶ and R²⁹ to R³² are independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R²⁹ to R³² are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents.

[0030] Another embodiment of the present invention provides apolymerisation catalyst comprising (1) a nitrogen-containing transitionmetal compound of Formula W and (2) an activating quantity of anactivator compound selected from organoaluminium compounds andhydrocarbylboron compounds,

[0031]  wherein X represents an atom or group covalently or ionicallybonded to the cobalt atom; T is the oxidation state of the cobalt atomand can be Co[I], Co[II], Co[III], and b is the valency of the atom orgroup X; R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and when any two ormore of R¹-R⁷ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents.

[0032] In the catalysts of the present invention the transition metal Min the nitrogen-containing complex is preferably Fe(II) or Co(II).

[0033] Each of the nitrogen atoms N¹, N² and N³ is coordinated to thetransition metal M by a “dative” bond, ie a bond formed by donation of alone pair of electrons from the nitrogen atom. The remaining bonds oneach nitrogen atom are covalent bonds formed by electron sharing betweenthe nitrogen atoms and the organic ligand as shown in the definedformulae for the transition metal complexes illustrated above.

[0034] The atom or group represented by X in the compounds of FormulaeB, Z, T and W can be, for example, selected from halide, sulphate,nitrate, thiolate, thiocarboxylate, BF₄ ⁻;, PF₆ ⁻, hydride,hydrocarbyloxide, carboxylate, hydrocarbyl, substituted hydrocarbyl andheterohydrocarbyl. Examples of such atoms or groups are chloride,bromide, methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, benzyl,methoxide, ethoxide, isopropoxide, tosylate, triflate, formate, acetate,phenoxide and benzoate. Preferred examples of the atom or group X in thecompounds of Formula B, Z, T and W are halide, for example, chloride,bromide; hydride; hydrocarbyloxide, for example, methoxide, ethoxide,isopropoxide, phenoxide; carboxylate, for example, formate, acetate,benzoate; hydrocarbyl, for example, methyl, ethyl, propyl, butyl, octyl,decyl, phenyl, benzyl; substituted hydrocarbyl; heterohydrocarbyl;tosylate; and triflate. Preferably X is selected from halide, hydrideand hydrocarbyl. Chloride is particularly preferred.

[0035] The following are examples of nitrogen-containing transitionmetal complexes that can be employed in the catalyst of the presentinvention:

[0036] 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl₂

[0037] 2,6-diacetylpyridine(2,6-diisopropylanil)MnCl₂

[0038] 2,6-diacetylpyridine(2,6-diisopropylanil)CoCl₂

[0039] 2,6-diacetylpyridinebis(2-tert.-butylanil)FeCl₂

[0040] 2,6-diacetylpyridinebis(2,3-dimethylanil)FeCl₂

[0041] 2,6-diacetylpyridinebis(2-methylanil)FeCl₂

[0042] 2,6-diacetylpyridinebis(2,4-dimethylanil)FeCl₂

[0043] 2,6-diacetylpyridinebis(2,6-dimethylanil)FeCl₂

[0044] 2,6-diacetylpyridinebis(2,4,6 trimethyl anil)FeCl₂

[0045] 2,6-dialdiminepyridinebis(2,6-dimethylanil)FeCl₂

[0046] 2,6-dialdiminepyridinebis(2,6-diethylanil)FeCl₂

[0047] 2,6-dialdiminepyridinebis(2,6-diisopropylanil)FeCl₂

[0048] 2,6-dialdiminepyridinebis(1-naphthil)FeCl₂ and

[0049] 2,6-bis(1,1-diphenylhydrazone)pyridine.FeCl₂.

[0050] A preferred complex of the present invention is2,6-diacetylpyridinebis(2,4,6 trimethyl anil)FeCl₂.

[0051] The activator compound for the catalyst of the present inventionis suitably selected from organoaluminium compounds and hydrocarbylboroncompounds. Suitable organoaluminium compounds include trialkyaluminiumcompounds, for example, trimethylaluminium, triethylaluminium,tributylaluminium, tri-n-octylaluminium, ethylaluminium dichloride,diethylaluminium chloride and alumoxanes. Alumoxanes are well known inthe art as typically the oligomeric compounds which can be prepared bythe controlled addition of water to an alkylaluminium compound, forexample trimethylaluminium. Such compounds can be linear, cyclic ormixtures thereof. Commercially available alumoxanes are generallybelieved to be mixtures of linear and cyclic compounds. The cyclicalumoxanes can be represented by the formula [R¹⁶ AlO]_(s) and thelinear alumoxanes by the formula R¹⁷(R¹⁸AlO)_(s) wherein s is a numberfrom about 2 to 50, and wherein R¹⁶, R¹⁷, and R¹⁸ represent hydrocarbylgroups, preferably C₁ to C₆ alkyl groups, for example methyl, ethyl orbutyl groups.

[0052] Examples of suitable hydrocarbylboron compounds aredimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate,triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate,sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate,H⁺(OEt₂)[(bis-3,5-trifluoromethyl)phenyl]borate,trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.

[0053] In the preparation of the catalysts of the present invention thequantity of activating compound selected from organoaluminium compoundsand hydrocarbylboron compounds to be employed is easily determined bysimple testing, for example, by the preparation of small test sampleswhich can be used to polymerise small quantities of the monomer(s) andthus to determine the activity of the produced catalyst. It is generallyfound that the quantity employed is sufficient to provide 0.1 to 20,000atoms, preferably 1 to 2000 atoms of aluminium or boron per Fe, Co, Mnor Ru metal atom in the compound of Formula B, Z, T or W.

[0054] In the compound of Formula B of the present invention, M ispreferably Fe[II]. In the compounds of Formula Z or Formula T of thepresent invention, M is preferably Fe[II], Mn[II] or Co[II].

[0055] A further aspect of the present invention provides apolymerisation catalyst system comprising (I) as the transition metalcompound, a compound having the Formula B, Z, T or W (2) an activatingquantity of an activator compound selected from organoaluminium andhydrocarbylboroncompounds and (3) a neutral Lewis base.

[0056] In this further aspect of the present invention, the iron andcobalt compounds are preferred. The preferences in relation to theactivator compound are the same as expressed above in relation to thecatalysts of the present invention. Neutral Lewis bases are well knownin the art of Ziegler-Natta catalyst polymerisation technology. Examplesof classes of neutral Lewis bases suitably employed in the presentinvention are unsaturated hydrocarbons, for example, alkenes (other than1-olefins) or alkynes, primary, secondary and tertiary amines, amides,phosphoramides, phosphines, phosphites, ethers, thioethers, nitriles,carbonyl compounds, for example, esters, ketones, aldehydes, carbonmonoxide and carbon dioxide, sulphoxides, sulphones and boroxines.Although 1-olefins are capable of acting as neutral Lewis bases, for thepurposes of the present invention they are regarded as monomer orcomonomer 1-olefins and not as neutral Lewis bases per se. However,alkenes which are internal olefins, for example, 2-butene andcyclohexene are regarded as neutral Lewis bases in the presentinvention. Preferred Lewis bases are tertiary amines and aromaticesters, for example, dimethylaniline, diethylaniline, tributylamine,ethylbenzoate and benzylbenzoate. In this particular aspect of thepresent invention, components (1), (2) and (3) of the catalyst systemcan be brought together simultaneously or in any desired order. However,if components (2) and (3) are compounds which interact togetherstrongly, for example, form a stable compound together, it is preferredto bring together either components (1) and (2) or components (1) and(3) in an initial step before introducing the final defined component.Preferably components (1) and (3) are contacted together beforecomponent (2) is introduced. The quantities of components (1) and (2)employed in the preparation of this catalyst system are suitably asdescribed above in relation to the catalysts of the present invention.The quantity of the neutral Lewis Base [component (3)] is preferablysuch as to provide a ratio of component (1):component (3) in the range100:1 to 1:1000, most preferably in the range 1:1 to 1:20. Components(1), (2) and (3) of the catalyst system can brought together, forexample, as the neat materials, as a suspension or solution of thematerials in a suitable diluent or solvent (for example a liquidhydrocarbon), or, if at least one of the components is volatile, byutilising the vapour of that component. The components can be broughttogether at any desired temperature. Mixing the components together atroom temperature is generally satisfactory. Heating to highertemperatures eg up to 120° C. can be carried out if desired, eg toachieve better mixing of the components. It is preferred to carry outthe bringing together of components (1), (2) and (3) in an inertatmosphere (eg dry nitrogen) or in vacuo. If it is desired to use thecatalyst on a support material (see below), this can be achieved, forexample, by preforming the catalyst system comprising components (1),(2) and (3) and impregnating the support material preferably with asolution thereof, or by introducing to the support material one or moreof the components simultaneously or sequentially. If desired the supportmaterial itself can have the properties of a neutral Lewis base and canbe employed as, or in place of, component (3). An example of a supportmaterial having neutral Lewis base properties is poly(aminostyrene) or acopolymer of styrene and aminostyrene (ie vinylaniline).

[0057] The catalysts of the present invention can if desired comprisemore than one of the defined transition metal compounds. The catalystmay comprise, for example a mixture of2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl₂ complex and2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ complex, or a mixtureof 2,6-diacetylpyridine(2,6-diisopropylanil)CoCl₂ and2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂. In addition to saidone or more defined transition metal compounds, the catalysts of thepresent invention can also include one or more other types of transitionmetal compounds or catalysts, for example, transition metal compounds ofthe type used in conventional Ziegler-Natta catalyst systems,metallocene-based catalysts, or heat activated supported chromium oxidecatalysts (eg Phillips-type catalyst).

[0058] The catalysts of the present invention can be unsupported orsupported on a support material, for example, silica, alumina, orzirconia, or on a polymer or prepolymer, for example polyethylene,polystyrene, or poly(aminostyrene).

[0059] Thus a preferred embodiment of the present invention provides acatalyst comprising

[0060] (1) a nitrogen-containing transition metal compound having thefollowing Formula B, and

[0061] (2) an activating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

[0062]  wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Ru[II],Ru[III], Ru[IV], Mn[I], Mn[II], Mn[III] or Mn[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹. R², R³, R⁴, and R⁶ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and such that (1):

[0063]  when M is Fe, Co or Ru, R⁵ and R⁷ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and when any two ormore of R¹-R⁷ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents, or such that (2):

[0064]  when M is Fe, Co, Mn or Ru, then R⁵ is represented by the group“P” and R⁷ is represented by the group “Q” as follows:

[0065]  wherein R¹⁹ to R²⁸ are independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ andR¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbylor substituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents; with the proviso that at least one ofR¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl when neither of thering systems P and Q forms part of a polyaromatic fused-ring system, orsuch that (3)

[0066]  when M is Fe, Co, Mn or Ru, then R⁵ is a group having theformula —NR²⁹R³⁰ and R⁷ is a group having the formula —NR³¹R³², whereinR²⁹ to R³² are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and R²⁹ to R³²are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents,

[0067] characterised in that the catalyst is supported on a supportmaterial.

[0068] If desired the catalysts can be formed in situ in the presence ofthe support material, or the support material can be pre-impregnated orpremixed, simultaneously or sequentially, with one or more of thecatalyst components. The catalysts of the present invention can ifdesired be supported on a heterogeneous catalyst, for example, amagnesium halide supported Ziegler Natta catalyst, a Phillips type(chromium oxide) supported catalyst or a supported metallocene catalyst.Formation of the supported catalyst can be achieved for example bytreating the transition metal compounds of the present invention withalumoxane in a suitable inert diluent, for example a volatilehydrocarbon, slurrying a particulate support material with the productand evaporating the volatile diluent. The produced supported catalyst ispreferably in the form of a free-flowing powder. The quantity of supportmaterial employed can vary widely, for example from 100,000 to 1 gramsper gram of metal present in the transition metal compound.

[0069] The present invention further provides a process for thepolymerisation and copolymerisation of 1-olefins comprising contactingthe monomeric olefin under polymerisation conditions with thepolymerisation catalyst of the present invention.

[0070] In the polymerisation process of the present invention thepolymerisation catalyst is preferably based on the Formula B, T, W or Zcompounds as described above.

[0071] The polymerisation conditions can be, for example, solutionphase, slurry phase or gas phase. If desired, the catalyst can be usedto polymerise ethylene under high pressure/high temperature processconditions wherein the polymeric material forms as a melt insupercritical ethylene. Preferably the polymerisation is conducted undergas phase fluidised bed conditions.

[0072] Slurry phase polymerisation conditions or gas phasepolymerisation conditions are particularly useful for the production ofhigh density grades of polyethylene. In these processes thepolymerisation conditions can be batch, continuous or semi-continuous.In the slurry phase process and the gas phase process, the catalyst isgenerally fed to the polymerisation zone in the form of a particulatesolid. This solid can be, for example, an undiluted solid catalystsystem formed from a nitrogen-containing complex and an activator, orcan be the solid complex alone. In the latter situation, the activatorcan be fed to the polymerisation zone, for example as a solution,separately from or together with the solid complex. Preferably thecatalyst system or the transition metal complex component of thecatalyst system employed in the slurry polymerisation and gas phasepolymeriastion is supported on a support material. Most preferably thecatalyst system is supported on a support material prior to itsintroduction into the polymerisation zone. Suitable support materialsare, for example, silica, alumina, zirconia, talc, kieselguhr, ormagnesia. Impregnation of the support material can be carried out byconventional techniques, for example, by forming a solution orsuspension of the catalyst components in a suitable diluent or solvent,and slurrying the support material therewith. The support material thusimpregnated with catalyst can then be separated from the diluent forexample, by filtration or evaporation techniques.

[0073] In the slurry phase polymerisation process the solid particles ofcatalyst, or supported catalyst, are fed to a polymerisation zone eitheras dry powder or as a slurry in the polymerisation diluent. Preferablythe particles are fed to a polymerisation zone as a suspension in thepolymerisation diluent. The polymerisation zone can be, for example, anautoclave or similar reaction vessel, or a continuous loop reactor, egof the type well-know in the manufacture of polyethylene by the PhillipsProcess. When the polymerisation process of the present invention iscarried out under slurry conditions the polymerisation is preferablycarried out at a temperature above 0° C., most preferably above 15° C.The polymerisation temperature is preferably maintained below thetemperature at which the polymer commences to soften or sinter in thepresence of the polymerisation diluent. If the temperature is allowed togo above the latter temperature, fouling of the reactor can occur.Adjustment of the polymerisation within these defined temperature rangescan provide a useful means of controlling the average molecular weightof the produced polymer. A further useful means of controlling themolecular weight is to conduct the polymerisation in the presence ofhydrogen gas which acts as chain transfer agent. Generally, the higherthe concentration of hydrogen employed, the lower the average molecularweight of the produced polymer.

[0074] The use of hydrogen gas as a means of controlling the averagemolecular weight of the polymer or copolymer applies generally to thepolymerisation process of the present invention. For example, hydrogencan be used to reduce the average molecular weight of polymers orcopolymers prepared using gas phase, slurry phase or solution phasepolymerisation conditions. The quantity of hydrogen gas to be employedto give the desired average molecular weight can be determined by simple“trial and error” polymerisation tests.

[0075] The polymerisation process of the present invention providespolymers and copolymers, especially ethylene polymers, at remarkablyhigh productivity (based on the amount of polymer or copolymer producedper unit weight of nitrogen-containing transition metal complex employedin the catalyst system). This means that relatively very smallquantities of transition metal complex are consumed in commercialprocesses using the process of the present invention. It also means thatwhen the polymerisation process of the present invention is operatedunder polymer recovery conditions that do not employ a catalystseparation step, thus leaving the catalyst, or residues thereof, in thepolymer (eg as occurs in most commercial slurry and gas phasepolymerisation processes), the amount of transition metal complex in theproduced polymer can be very small. Experiments carried out with thecatalyst of the present invention show that, for example, polymerisationof ethylene under slurry polymerisation conditions can provide aparticulate polyethylene product containing catalyst so diluted by theproduced polyethylene that the concentration of transition metal thereinfalls to, for example, 1 ppm or less wherein “ppm” is defined as partsby weight of transition metal per million parts by weight of polymer.Thus polyethylene produced within a polymerisation reactor by theprocess of the present invention may contain catalyst diluted with thepolyethylene to such an extent that the transition metal content thereofis, for example, in the range of 1-0.001 ppm, preferably 1-0.001 ppm.Using a catalyst comprising a nitrogen-containing Fe complex inaccordance with the present invention in, for example, a slurrypolymerisation, it is possible to obtain polyethylene powder wherein theFe concentration is, for example, 1.03 to 0.11 parts by weight of Fe permillion parts by weight of polyethylene.

[0076] Suitable monomers for use in the polymerisation process of thepresent invention are, for example, ethylene, propylene, butene, hexene,methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile,vinyl acetate, and styrene. Preferred monomers for homopolymerisationprocesses are ethylene and propylene. The catalyst can also be used forcopolymerising ethylene with other 1-olefins such as propylene,1-butene, 1-hexene, 4-methylpentene-1, and octene.

[0077] Thus the present invention further provides a process comprisingcontacting ethylene and one or more other 1-olefins with a catalystcomprising

[0078] (1) a nitrogen-containing transition metal compound having thefollowing Formula B, and

[0079] (2) an activating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

[0080]  wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Ru[II],Ru[III], Ru[IV], Mn[I], Mn[II], Mn[III] or Mn[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹, R², R³, R⁴, and R⁶ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and such that (1):

[0081]  when M is Fe, Co or Ru, R⁵ and R⁷ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and when any two ormore of R¹-R⁷ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents, or such that (2):

[0082]  when M is Fe, Co, Mn or Ru, then R⁵ is represented by the group“P” and R⁷ is represented by the group “Q” as follows:

[0083]  wherein R¹⁹ to R²⁸ are independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ andR¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbylor substituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents; with the proviso that at least one ofR¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl when neither of thering systems P and Q forms part of a polyaromatic fused-ring system, orsuch that (3)

[0084]  when M is Fe, Co, Mn or Ru, then R⁵ is a group having theformula —NR²⁹R³⁰ and R⁷ is a group having the formula —NR³¹R³², whereinR²⁹ to R³² are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and Re to R³²are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents.

[0085] The catalyst of the present invention can also be used forcopolymerising ethylene with other monomeric materials, for example,methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile,vinyl acetate, and styrene.

[0086] A preferred embodiment of the present invention comprises aprocess for the polymerisation and copolymerisation of 1-olefinscomprising contacting the monomeric olefin under polymerisationconditions with a polymerisation catalyst comprising

[0087] (1) a nitrogen-containing transition metal compound having thefollowing Formula B, and

[0088] (2) an activating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

[0089]  wherein M is Fe[II], Fe[III], Co[I], Co[III], Co[II], Ru[II],Ru[III], Ru[IV], Mn[I], Mn[II], Mn[III] or Mn[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹, R², R³, R⁴, and R⁶ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and such that (1):

[0090]  when M is Fe, Co or Ru, R⁵ and R⁷ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and when any two ormore of R¹-R⁷ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents, or such that (2):

[0091]  when M is Fe, Co, Mn or Ru, then R⁵ is represented by the group“P” and R⁷ is represented by the group “Q” as follows:

[0092]  wherein R¹⁹ to R²⁸ are independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ andR¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbylor substituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents; with the proviso that at least one ofR¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl when neither of thering systems P and Q forms part of a polyaromatic fused-ring system, orsuch that (3)

[0093]  when M is Fe, Co, Mn or Ru, then R⁵ is a group having theformula —NR²⁹R³⁰ and R⁷ is a group having the formula —NR³¹R³², whereinR²⁹ to R³² are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and R²⁹ to R³²are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents

[0094] characterised in that the polymerisation conditions are gas phasepolymerisation conditions.

[0095] Methods for operating gas phase polymerisation processes are wellknown in the art. Such methods generally involve agitating (eg bystirring, vibrating or fluidising) a bed of catalyst, or a bed of thetarget polymer (ie polymer having the same or similar physicalproperties to that which it is desired to make in the polymerisationprocess) containing a catalyst, and feeding thereto a stream of monomerat least partially in the gaseous phase, under conditions such that atleast part of the monomer polymerises in contact with the catalyst inthe bed. The bed is generally cooled by the addition of cool gas (egrecycled gaseous monomer) and/or volatile liquid (eg a volatile inerthydrocarbon, or gaseous monomer which has been condensed to form aliquid). The polymer produced in, and isolated from, gas phase processesforms directly a solid in the polymerisation zone and is free from, orsubstantially free from liquid. As is well known to those skilled in theart, if any liquid is allowed to enter the polymerisation one of a gasphase polymerisation process the quantity of liquid is small in relationto the quantity of polymer present in the polymerisation zone. This isin contrast to “solution phase” processes wherein the polymer is formeddissolved in a solvent, and “slurry phase” processes wherein the polymerforms as a suspension in a liquid diluent.

[0096] The gas phase process can be operated under batch, semi-batch, orso-called “continuous” conditions. It is preferred to operate underconditions such that monomer is continuously recycled to an agitatedpolymerisation zone containing polymerisation catalyst, make-up monomerbeing provided to replace polymerised monomer, and continuously orintermittently withdrawing produced polymer from the polymerisation zoneat a rate comparable to the rate of formation of the polymer, freshcatalyst being added to the polymerisation zone to replace the catalystwithdrawn form the polymerisation zone with the produced polymer.

[0097] In the preferred embodiment of the gas phase polymerisationprocess of the present invention, the gas phase polymerisationconditions are preferably gas phase fluidised bed polymerisationconditions.

[0098] Methods for operating gas phase fluidised bed processes formaking polyethylene and ethylene copolymers are well known in the art.The process can be operated, for example, in a vertical cylindricalreactor equipped with a perforated distribution plate to support the bedand to distribute the incoming fluidising gas stream through the bed.The fluidising gas circulating through the bed serves to remove the heatof polymerisation from the bed and to supply monomer for polymerisationin the bed. Thus the fluidising gas generally comprises the monomer(s)normally together with some inert gas (eg nitrogen) and optionally withhydrogen as molecular weight modifier. The hot fluidising gas emergingfrom the top of the bed is led optionally through a velocity reductionzone (this can be a cylindrical portion of the reactor having a widerdiameter) and, if desired, a cyclone and or filters to disentrain finesolid particles from the gas stream. The hot gas is then led to a heatexchanger to remove at least part of the heat of polymerisation.Catalyst is preferably fed continuously or at regular intervals to thebed. At start up of the process, the bed comprises fluidisable polymerwhich is preferably similar to the target polymer. Polymer is producedcontinuously within the bed by the polymerisation of the monomer(s).Preferably means are provided to discharge polymer from the bedcontinuously or at regular intervals to maintain the fluidised bed atthe desired height. The process is generally operated at relatively lowpressure, for example, at 10 to 50 bars, and at temperatures forexample, between 50 and 120° C. The temperature of the bed is maintainedbelow the sintering temperature of the fluidised polymer to avoidproblems of agglomeration.

[0099] In the gas phase fluidised bed process for polymerisation ofolefins the heat evolved by the exothermic polymerisation reaction isnormally removed from the polymerisation zone (ie, the fluidised bed) bymeans of the fluidising gas stream as described above. The hot reactorgas emerging from the top of the bed is led through one or more heatexchangers wherein the gas is cooled. The cooled reactor gas, togetherwith any make-up gas, is then recycled to the base of the bed. In thegas phase fluidised bed polymerisation process of the present inventionit is desirable to provide additional cooling of the bed (and therebyimprove the space time yield of the process) by feeding a volatileliquid to the bed under conditions such that the liquid evaporates inthe bed thereby absorbing additional heat of polymerisation from the bedby the “latent heat of evaporation” effect. When the hot recycle gasfrom the bed enters the heat exchanger, the volatile liquid can condenseout. In one embodiment of the present invention the volatile liquid isseparated from the recycle gas and reintroduced separately into the bed.Thus, for example, the volatile liquid can be separated and sprayed intothe bed. In another embodiment of the present invention the volatileliquid is recycled to the bed with the recycle gas. Thus the volatileliquid can be condensed from the fluidising gas stream emerging from thereactor and can be recycled to the bed with recycle gas, or can beseparated from the recycle gas and sprayed back into the bed.

[0100] The method of condensing liquid in the recycle gas stream andreturning the mixture of gas and entrained liquid to the bed isdescribed in EP-A-0089691 and EP-A-0241947. It is preferred toreintroduce the condensed liquid into the bed separate from the recyclegas using the process described in our U.S. Pat. No. 5,541,270, theteaching of which is hereby incorporated into this specification.

[0101] When using the catalysts of the present invention under gas phasepolymerisation conditions, the catalyst, or one or more of thecomponents employed to form the catalyst can, for example, be introducedinto the polymerisation reaction zone in liquid form, for example, as asolution in an inert liquid diluent. Thus, for example, the transitionmetal component, or the activator component, or both of these componentscan be dissolved or slurried in a liquid diluent and fed to thepolymerisation zone. Under these circumstances it is preferred theliquid containing the component(s) is sprayed as fine droplets into thepolymerisation zone. The droplet diameter is preferably within the range1 to 1000 microns. EP-A-0593083, the teaching of which is herebyincorporated into this specification, discloses a process forintroducing a polymerisation catalyst into a gas phase polymerisation.The methods disclosed in EP-A-0593083 can be suitably employed in thepolymerisation process of the present invention if desired.

[0102] The present invention further provides a novelnitrogen-containing transition metal compound comprising the skeletalunit depicted in Formula Z:

[0103] wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I],Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X, R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents; with the proviso thatat least one of R¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl whenneither of the ring systems P and Q forms part of a polyaromaticfused-ring system. In this particular aspect of the present invention,in the case that neither of the ring systems P and Q forms part of apolyaromatic ring system, it is preferred that at least one of R¹⁹ andR²⁰, and at least one of R²¹ and R²² is selected from hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl. In one embodiment of the present invention, R¹⁹, R²⁰,R²¹ and R²² are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbylor substituted heterohydrocarbyl when neither of the ring systems P andQ forms part of a polyaromatic fused-ring system.

[0104] Subject to the foregoing provisos regarding R¹⁹, R²⁰, R²¹ and R²²in Formula Z, R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ in the compounds depicted inFormulae B and Z of the present invention are preferably independentlyselected from hydrogen and C₁ to C₈ hydrocarbyl, for example, methyl,ethyl, n-propyl, n-butyl, n-hexyl, and n-octyl. In Formula B, R⁵ and R⁷are preferably independently selected from substituted or unsubstitutedalicyclic, heterocyclic or aromatic groups, for example, phenyl,1-naphthyl, 2-naphthyl, 2-methylphenyl, 2-ethylphenyl,2,6-diisopropylphenyl, 2,3-diisopropylphenyl, 2,4-diisopropylphenyl,2,6-di-n-butylphenyl, 2,6-dimethylphenyl, 2,3-dimethylphenyl.2,4-dimethylphenyl, 2-t-butylphenyl, 2,6-diphenylphenyl,2,4,6-trimethylphenyl, 2,6-trifluoromethylphenyl,4-bromo-2,6-dimethylphenyl, 3,5 dichloro2,6diethylphenyl, and2,6,bis(2,6-dimethylphenyl)phenyl, cyclohexyl and pyridinyl.

[0105] The ring systems P and Q in Formula Z are preferablyindependently 2,6-hydrocarbylphenyl or fused-ring polyaromatic, forexample, 1-naphthyl, 2-naphthyl, 1-phenanthrenyl and 8-quinolinyl.

[0106] Yet another aspect of the present invention provides a novelnitrogen-containing transition metal compound comprising the skeletalunit depicted in Formula T:

[0107] wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I],Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹ to R⁴, R⁶ and R²⁹ to R³² are independentlyselected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R² to R³² are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents.

[0108] A further aspect of the invention comprises the use of thecompounds defined previously as catalysts for the polymerisation orco-polymerisation of 1-olefins.

[0109] The following are examples of novel nitrogen-containingtransition metal complexes of the present invention:

[0110] 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl₂

[0111] 2,6-diacetylpyridine(2,6-diisopropylanil)MnCl₂

[0112] 2,6-diacetylpyridine(2,6-disopropylanil)CoCl₂

[0113] 2,6-diacetylpyridinebis(2-tert.-butylanil)FeCl₂

[0114] 2,6-diacetylpyridinebis(2,3-dimethylanil)FeCl₂

[0115] 2,6-diacetylpyridinebis(2-methylanil)FeCl₂

[0116] 2,6-diacetylpyridinebis(2,4-dimethylanil)FeCl₂

[0117] 2,6-diacetylpyridinebis(2,6-dimethylanil)FeCl₂

[0118] 2,6-diacetylpyridinebis (2,4,6-trimethylanil)FeCl₂

[0119] 2,6-dialdiminepyridinebis(2,6-dimethylanil)FeCl₂

[0120] 2,6-dialdiminepyridinebis(2,6-diethylanil)FeCl₂

[0121] 2,6-dialdiminepyridinebis(2,6-diisopropylanil)FeCl₂

[0122] 2,6-dialdiminepyridinebis(1-naphthil)FeCl₂ and2,6-bis(1,1-diphenylhydrazone)pyridine.FeCl₂.

[0123] 2,6-diacetylpyridinebis (2,4,6-trimethylanil)FeCl₂ is preferred.

[0124] The present invention further provides novel compounds useful formaking polymerisation catalysts comprising a compound having the generalFormula E as follows:

[0125] wherein R¹⁰, R¹¹, R¹² and R¹³ are independently selected from C₁to C₂₀ hydrocarbon groups; and R¹⁴, R¹⁵ and all the remaining ringsubstituents on the pyridine and benzene rings depicted in Formula E areindependently selected from hydrogen and C₁ to C₂₀ hydrocarbon groups.

[0126] The production of ligands for preparing the nitrogen containingtransition metal complexes used in the present invention is conventionalsynthetic organic chemistry. For example, ligands of the type shownattached to the transition metal atom in Formula B can be made, forexample, by reacting together a substituted or unsubstituted2,6-dicarboxaldehydepyridine or 2,6-diacylpyridine compound (ie havingthe appropriate R¹, R², R³, R⁴ and R⁶ substituents) with two molarequivalents of a diamine bearing the desired substituents R⁵ and R⁷.

[0127] The present invention further provides novel compounds useful formaking polymerisation catalysts comprising a compound having the generalFormula P as follows:

[0128] wherein R¹ to R⁴, R⁶ and R²⁹ to R³² are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and Re to R³² are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents. Preferably R²⁹, R³⁰,R³¹ and R³² are hydrocarbyl. Most preferably at least one of R²⁹ andR³⁰, and at least one of R³¹ and R³² are aryl groups, for example,phenyl, naphthyl, or substituted phenyl. Ligands of the type shown inFormula P can be prepared by well-known methods, for example by reactionof a substituted or unsubstituted 2,6-di(carboxaldehyde)pyridine or2,6-diacylpyridine compound (ie having the appropriate R¹, R², R³, R⁴and R⁶ substituents) with two molar equivalents of a hydrazine compoundbearing the desired substituents R²⁹, R³⁰, R³¹ and R³².

[0129] Thus ligands of the type illustrated, for example, in Formulae B,Z, T, E and P can generally be prepared by condensation reactionsbetween bis(carbonyl)pyridine compounds and appropriate amines orhydrazines. Such reactions can be catalysed, for example, by acids, forexample, acetic acid or toluene-p-sulphonic acid. During reactions ofthis type it is normally advantageous to remove from the reaction zonethe water eliminated by the reaction of the carbonyl groups with the—NH₂ groups. In the preparation of ligands using this type of reaction,it is preferred to take off the water by refluxing the reaction mixturewith an azeotrope-forming water-immiscible liquid, and separating andremoving the water from the distillate in a suitable reflux head, eg ina Dean and Stark head. Suitable liquids for this purpose are, forexample, hydrocarbons, especially aromatic hydrocarbons such as tolueneor xylene.

[0130] The present invention is illustrated in the following Examples.

EXAMPLES

[0131] Example 1 shows the preparation of an iron compound (see FormulaD below), Example 2 shows the preparation of a manganese compound (seeFormula J below) and Example 3 shows the preparation of a cobaltcompound (see Formula K), for preparing the catalyst of the presentinvention. Runs 1.1 to 1.6, 2.1, 3.1 and 3.2 illustrate the use of thesecompounds as catalysts in the polymerisation of ethylene in accordancewith the catalyst and process of the present invention.

[0132] In the Examples all manipulations of air/moisture-sensitivematerials were performed on a conventional vacuum/inert atmosphere(nitrogen) line using standard Schlenk line techniques, or in an inertatmosphere glove box.

Example 1

[0133] Intermediate A [2,6-diacetylpyridinebis(2,6-diisopropylanil)] wasprepared by the reaction of Intermediate B [2,6-diacetylpyridine] andIntermediate C [2,6-diisopropylaniline]. Intermediate A was then reactedwith ferrous chloride in butanol to provide the compound of Formula D.

[0134] Preparation of Intermediate A

[0135] Using a procedure based on a related preparation (E. C. Alyea andP. H. Merrell, Synth. React. Inorg. Metal-Org. Chem., 1974, 4,535):-2,6-diisopropylanuine (3.46 ml, 18.4 mmol) was added dropwise to asolution of 2,6-diacetylpyridine (1.50 g, 9.2 mmol) in absolute ethanol(25 ml) [2,6-diisopropylaniline and 2,6-diacetylpyridine were obtainedfrom Aldrich the former of which was freshly distilled before use]. Afew drops of glacial acetic acid was added and the solution was refluxedfor 48 h. Concentration of the solution to half volume and cooling to−78° C. gave intermediate A as pale yellow crystals (80%). Calcd forC₃₃H₄₃N₃: C, 82.3; H 8.9; N, 8.7; Found: C, 81.9; H. 8.5; 8.7%. FABMS:M+(481). ¹H NMR (CDCl₃): 8.6-7.9[m, 3H, C₅H₃N], 7.2-6.9[m, 6H,C₆(CHMe₂)H₃], 2.73[sept, 4H, CHMe₂], 2.26[s, 6H, C₅H₃N(CMeNAr)₂] and1.16 [m, 24H, CHMe₂]. FABMS is fast atom bombardment mass spectrometry.

[0136] Preparation of the Formula D Compound[2.6-diacetylpyridinebis(2.6-diisopropylanil)FeCl₂]

[0137] FeCl₂ (0.24 g; 1.89 mmol) was dissolved in hot n-butanol (20 ml)at 80° C. A suspension of 2,6-diacetylpyfidinebis(2,6-diisopropylanil)(0.92 g; 1.89 mmol) in n-butanol was added dropwise at 80° C. Thereaction mixture turned blue. After stirring at 80° C. for 15 minutesthe reaction was allowed to cool down to room temperature. The reactionvolume was reduced to a few ml, and petroleum ether (40/60) was added toprecipitate the product (a blue powder), which was subsequently washedthree times with 10 ml petroleum ether (40/60). The yield was 0.93 g(81%).

[0138] Mass spectrum: m/z 607 [M]+, 572 [M-Cl]+, 482 [M-FeCl₂]+.

[0139] Analysis—Calculated: for C₃₃H₃N₃FeCl₂: C, 65.14; H. 7.12; N,6.91. Found: C, 64.19; H, 6.90; N, 6.70.

[0140] Runs 1.1 to 1.6—Polymerisation Tests

[0141] The polymerisation tests described in Runs 1.1 to 1.6 were werecarried out using the following procedure. The catalyst of Formula D andcocatalyst (methylalumoxane—“MAO”) was added to a Schlenk tube anddissolved in toluene (40 ml). The tube was purged with ethylene and thecontents were mechanically stirred and maintained under 1 bar ethylenefor the duration of the polymerisation. After half an hour thepolymerisation was terminated by the addition of aqueous hydrogenchloride. The produced solid polyethylene was filtered off, washed withmethanol and dried in a vacuum oven at 50° C. In Run 1.1, some toluenesoluble polyethylene was recovered from the filtrate by separating thetoluene layer, drying over MgSO₄, and evaporating the solvent.

[0142] The results of the polymerisation tests are summarised in thefollowing Table.

[0143] It will be seen from the Table that the iron compound catalystprovided high activity in the polymerisation of ethylene usingmethylalumoxane as cocatalyst, but that use of diethylaluminiumchlorideas cocatalyst (Run 1.4) gave poor activity. The use of a cocatalystconsisting of a perfluorophenylboron compound with triisobutylaluminiumgave moderately high activity. TABLE Cocatalyst/ Catalyst Quantity PE(soluble) Activity Example mmol (Note 1) PE solid (Note 2) (Note 3) 1.10.05 MAO/400 12.0 g 0.78 g  480 1.2 0.025 MAO/400  8.0 g nd  640 1.30.025 MAO/400  9.7 g nd  780 1.4 0.025 DEAC/400  0.01 g 0 low 1.5 0.025See Note 4  3.5 g 0  280 1.6 0.01 MAO/100  5.7 g nd 1130

[0144] Notes on the Table

[0145] 1 MAO is methylalumoxane (cocatalyst). DEAC is diethylaluminiumchloride. The “Quantity” units are milliequivalents based on atoms ofaluminium. The MAO was supplied by Aldrich except in Run 1.3 in whichthe MAO was prepared according to the method provided by Gianetti, E.;Nicoletti, G. M.; Mazzocchi, R. Journal of Polymer Science: Part A;Polymer Chemistry 1985, 23, 2117-2133.

[0146] 2. Recovered from the toluene reaction medium.

[0147] 3. The activity is expressed as g mmol⁻¹ h⁻¹ bar⁻¹ (grams ofpolymer produced per millimole of catalyst per hour per bar pressure ofethylene).

[0148] 4. In Run 1.5, the cocatalyst was provided by 1 millequivalent oftris(perfluorophenyl)boron and 20 milliequivalents oftriisobutylaluminium.

Example 2

[0149] The manganese[II] compound illustrated in the following diagramwas prepared and tested for catalytic activity in the polymerisation ofethylene.

[0150] Preparation of Manganese(II) compound with Formula J[(2.6-diacetylpyridine(2.6-diisopropylanil)MnCl₂]

[0151] A suspension of MnCl₂.4H₂O (0.50 g, 2.53 mmol) and Intermediate A(1.22 g, 2.53 mmol) was refluxed in acetonitrile (50 ml) for 12 h togive an orange solution. On cooling to room temperature orange crystalswere obtained of the Mn(II) compound of Formula J; yield 59%.Microanalysis data supported the Formula J empirical formula. The FABmass spectrum displayed a highest peak corresponding to an M+—Cl (571)ion.

[0152] Polymerisation Test—Run 2.1

[0153] A 1.8 M solution of diethylaluminium chloride (DEAC) in toluene(0.50 ml, 0.9 mmol, 30 equivalents) was added via syringe to a stirredsuspension of the Formula J Mn(II) compound (18 mg, 0.03 mmol) intoluene (40 ml). The produced catalyst solution was degassed underreduced pressure and back-filled with an atmosphere of ethylene. Duringthe run time of 20 h the solution was left open to a supply of ethyleneat one atmosphere and stirred vigorously at 25° C. The polymerisationwas terminated by the addition of dilute HCl (ca. 40 ml) and thenstirred for 30 minutes to dissolve the alkylaluminium residues. Solidpolyethylene was filtered from the reaction, washed with an acidifiedmethanol solution and dried in vacuo at 40° C. overnight. Yield 0.011 g.Activity was 0.2 gmmol⁻1hr⁻1bar⁻1.

Example 3 Preparation of2.6-diacetylpyridine(2.6-diisopropylanil)CoCl₂-Formula K

[0154] Cobalt chloride (CoCl₂-0.057 g; 0.44 mmol) was dissolved in hotn-butanol (10 ml) at 80° C. A suspension of Intermediate A[2,6-diacetylpyridinebis(2,6-diisopropylanil)] (0.21 g; 0.44 mmol) inn-butanol was added dropwise at 8⁰° C. After stirring at 80° C. for 15minutes the produced reaction mixture was allowed to cool to roomtemperature. The reaction volume was reduced to a few ml and petroleumether (40/60) was added to precipitate the product. The olive greenpowdery precipitate was washed three times with 10 ml aliquots ofpetroleum ether (40/60). The yield of the cobalt complex (Formula K—seebelow) was 0.18 g (67% of theory). The mass spectrum showed m/z 575[M-Cl]⁺, 538 [M-2Cl]⁺

[0155] Polymerisation Tests—Runs 3.1 and 3.2

[0156] Polymerisation tests were carried out as described in Example 1except that the catalyst was the Formula K compound. The MAO employed(obtained from Aldrich—Catalogue No. 40,459-4) was a 10 weight %solution in toluene.

[0157] It will be seen from the Table that the Formula K catalyst whenactivated with MAO was highly active in the polymerisation of ethylene.TABLE Cocatalyst/ Catalyst Quantity Activity Example mmol (Note 5) PEsolid (Note 6) 3.1 0.05 MAO/100 5.2 g 207 3.2 0.01 MAO/100 2.3 g 464

[0158] Notes on the Table:.

[0159] 5. The “Quantity” units are milliequivalents based on atoms ofaluminium

[0160] 6. The activity is expressed as g mmol⁻¹ h⁻¹ bar⁻¹ (grams ofpolymer produced per millimole of catalyst per hour per bar pressure ofethylene).

Examples 4 to 9 Preparation of Iron Complexes Example 4

[0161] 4.1—Preparation of 2.6-diacetylpyridinebis(2-tert.-butylanil)

[0162] To a solution of 2,6-diacetylpyridine (0.54 g; 3.31 mmol) inabsolute ethanol (20 ml) was added 2-tertiarybutylaniline (1.23 g; 2.5eq.). After the addition of 2 drops of acetic acid (glacial) thesolution was refluxed overnight. Upon cooling to room temperature theproduct crystallised from ethanol. The product was filtered, washed withcold ethanol and dried in a vacuum oven (50° C.) overnight. The yieldwas 1.07 g (76%). Analysis ¹H NMR(CDCl₃): 8.43, 7.93, 7.44, 7.21, 7.09,6.56 (m, 7H, ArH, pyrH), 2.43 (s, 6H, N=CCH₃), 1.39 (s, 181, CCH₃).

[0163] 4.2—Preparation of2.6-diacetlpyridinebis(2-tert.-butylanil)FeCl₂.

[0164] FeCl₂ (0.15 g; 1.18 mmol) was dissolved in hot n-butanol (20 ml)at 80° C. A suspension of 2,6-diacetylpyridinebis(2-tert.-butylanil)(0.5 g; 1.18 mmol) in n-butanol was added dropwise at 80° C. Thereaction mixture turned blue. After stirring at 80° C. for 15 minutesthe reaction was allowed to cool down to room temperature. The reactionvolume was reduced to a few ml and diethyl ether was added toprecipitate the product as a blue powder, which was subsequently washedthree times with 10 ml diethyl ether. The yield was 0.55 g (85%).Analysis—Mass spectrum: m/z 551 [M]+, 516 [M-Cl]+, 426 [M-FeCl₂]+.

Example 5

[0165] 5.1—Preparation of 2.6-diacetylpyridinebis(2-methylanil)

[0166] The procedure was as for Example 4.1 except that 2-methyl anilinewas used instead of 2-tertiarybutylaniline. The yield was Yield: 0.42 g(33%)

[0167]¹H NMR(CDCl₃): 8.48 (d, 2H, pyrH), 7.91 (t, 11H, pyrH), 7.28 (in,41, ArH), 7.10 (m,2H, ArH), 6.75 (in, 2H. ArH), 2.42 (s, 6H, N=CCH₃),2.20 (s, 6H, CH₃).

[0168] 5.2—Preparation of 2.6-diacetylpyridinebis(2-methylanil)FeCl₂

[0169] The procedure was as for Example 4.2 except that2,6-diacetylpyridinebis(2-methylanil) was employed instead of2,6-diacetylpyridinebis(2-tert.-butylanil). The yield was 77% oftheoretical.

[0170] Mass spectrum: m/z 467 [M]⁺, 432 [M-Cl]⁺.

Example 6

[0171] 6.1—Preparation of 2.6-diacetylpyridinebis(2.3-dimethylanil)

[0172] The procedure was as for Example 4.1 except that 2,3-dimethylaniline was used instead of 2-tertiarybutylaniline. The yield was 80% oftheoretical.

[0173]¹HNMR(CDCl₃): 8.41, 7.89, 7.10, 6.94, 6.55, (m, 9H, ArH, pyrH),2.33 (m, 6H, N=CCH₃, 6H, CCH₃), 2.05 (s, 6H, CCH₃).

[0174] Mass spectrum: m/z 369 [M]⁺.

[0175] 6.2—Preparation of 2.6-diacetylpyridinebis(2.3-dimethylanil)FeCl₂

[0176] The procedure was as for Example 4.2 except that2,6-diacetylpyridinebis(2,3-dimethylanil) was employed instead of2,6-diacetylpyridinebis(2-tert.-butylanil).

[0177] The yield was 83% of theoretical.

[0178] Mass spectrum: m/z 496 [M]), 461 [M-Cl]⁺, 425 [M-Cl_(2]) ⁺.

Example 7

[0179] 7.1—Preparation of 2.6-diacetylpridinebis(2.4-dimethylanil)

[0180] The procedure was as for Example 4.1 except that 2,4-dimethylaniline was used instead of 2-tertiarybutylaniline. The yield was 75% oftheoretical.

[0181]¹H NMR(CDCl₃): 8.41, 7.90, 7.05, 6.90, 6.55, (m, 9H, ArH, pyrH),2.36 (m, 6H, N=CCH₃, 6K, CCH₃), 2.13 (s, 6H, CCH₃).

[0182] Mass spectrum: m/z 369 [M]⁺.

[0183] 7.2—Preparation of 2.6-diacetylpyridinebis(2.4-dimethylanil)FeCl₂

[0184] The procedure was as for Example 4.2 except that2,6-diacetylpyridinebis(2,4-dimethylanil) was employed instead of2,6-diacetylpyridinebis(2-tert.-butylanil).

[0185] The yield was 75% of theoretical.

[0186] Mass spectrum: m/z 496 [M]⁺, 461 [M-Cl]⁺, 425 [M-Cl₂]⁺.

Example 8

[0187] 8.1 Preparation of 2.6-diacetylpyridinebis(2.6-dimethylanil)

[0188] The procedure was as for Example 4.1 except that 2,6-dimethylaniline was used instead of 2-tertiarybutylaniline. The yield was 78% oftheoretical.

[0189]¹HNMR(CDCl₃): 8.48, 8.13, 7.98, 7.08, 6.65, (m, 9H, ArH, pyrH),2.25 (s, 6H, N=CCH₃), 2.05 (m, 12H, CCH₃).

[0190] Mass spectrum: m/z 369 [M]⁺.

[0191] 8.2—Preparation of 2.6-diacetylpyridinebis(2.6-dimethylanil)FeCl₂

[0192] The procedure was as for Example 4.2 except that2,6-diacetylpyridinebis(2,6-dimethylanil) was employed instead of2,6-diacetylpyridinebis(2-tert.-butylanil).

[0193] The yield was 78% of theoretical.

[0194] Mass spectrum: m/z 496 [M]⁺, 461 [M-Cl]⁺, 425 [M-Cl₂]⁺.

Example 9

[0195] 9.1 Preparation of 2.6-diacetylpyridinebis(2.4.6-trimethylanil)

[0196] The procedure was as for Example 4.1 except that 2,4,6-trimethylaniline was used instead of 2-tertiarybutylaniline. The yield was 60% oftheoretical.

[0197]¹H NMR(CDCl₃): 8.50, 7.95. 6.94, (m, 7H, ArH, pyrH), 2.33 (s, 6H,N=CCH₃), 2.28 (s, 6H, CCH₃), 2.05 (s, 12H, CCH₃).

[0198] Mass spectrum: m/z 397 [M]⁺.

[0199] 9.2—Preparation of2.6-diacetylpyridinebis(2.4.6-trimethylanil)FeCl₂

[0200] The procedure was as for Example 4.2 except that2,6-diacetylpyridinebis(2,4,6-trimethylanil) was employed instead of2,6-diacetylpyridinebis(2-tert.-butylanil).

[0201] The yield was 64% of theoretical.

[0202] Mass spectrum, m/z 523 [M]⁺, 488 [M-Cl]⁺, 453 [M-Cl₂]⁺.

Examples 4 to 9 Polymerisation Tests on Iron Complexes

[0203] The polymerisation tests were carried out using the followingprocedure. The catalysts (iron complexes) prepared in each of Examples 4to 9 and cocatalyst (methylalumoxane—“MAO”) was added to a Schlenk tubeand dissolved in toluene (40 ml). The “MAO” was used as a 10 wt %solution in toluene (supplied by Aldrich, catalogue number: 40,4594).The tube was purged with ethylene and the contents were mechanicallystirred and maintained under 1 bar ethylene for the duration of thepolymerisation. The polymerisation tests were each commenced at roomtemperature (20° C.). After half an hour the polymerisation wasterminated by the addition of aqueous hydrogen chloride. The producedsolid polyethylene was filtered off, washed with methanol and dried in avacuum oven at 50° C. The toluene soluble fraction (PE tol. sol.) wasisolated from the filtrate by separation of the toluene layer from theaqueous layer, drying over MgSO₄ and removal of the toluene bydistillation. GC/MS analysis showed that the toluene soluble fractionconsists of oligomeric products.

[0204] The results of the polymerisation tests are summarised in theTable 3. TABLE 3 Complex from PE Example Catalyst Cocatalyst/ solid PEtol. sol. Activity No. mmol equivalents grams grams g/mmolhbar 4.2 0.01MAO/100 5.01 — 1002 5.2 0.01 MAO/100 0.32 64 6.2 0.02 MAO/400 0.26 2.63289 7.2 0.02 MAO/400 1.20 120 8.2 0.02 MAO/400 5.7 566 9.2 0.01 MAO/1006.2 1230

[0205] Analysis for Solid Polyethylene Example No. Mn Mw PDI 4.2 4100228000 55.3 6.2 620 910 1.5 8.2 1900 29000 15.3 9.2 4400 52000 11.9

[0206] Analysis for toluene soluble polyethylene: Example No Mn Mw PDI6.2 300 410 1.4

Example 10

[0207] 10.0—Preparation of 2.6-pyridinedicarboxaldehyde

[0208] 2,6-Dimethanolpyridine (5.55 g, 0.040 mol—supplied by AldrichChemical Co.) and selenium dioxide (4.425 g, 0.040 mol, 1 equivalent)were dissolved in 1,4-dioxane (100 ml) and refluxed (4 h). The resultingmixture was filtered to yield a clear orange solution. The solvent wasremoved under vacuum and the product was recrystallised from chloroform:petroleum ether (40/60° C.) 1:1) to yield a white powder (7.44 g, 75%)

[0209] Analysis—Mass spectrum (CI) 136 [M+H]+, 153 [M+NH3]+

[0210]¹H NMR (250 Hz, CDCl₃) 10.17 (2H, s), 8.19 (2H, d, J=8.4 Hz), 8.17(1H, t, J=8.4 Hz)

[0211] 10,1—Preparation of 2,6-dialdiminepyridinebis(2,6-dimethylanil)

[0212] To the 2,6-pyridinedicarboxaldehyde (0.80 g, 5.93 mmol), preparedas described above, in absolute ethanol (50 ml), was added redistilled2,6-dimethylaniline (2.1 eq, 12.45 mmol, 1.5 ml) and glacial acetic acid(catalytic, 3 drops) and the resulting mixture was refluxed (24 h).Cooling and recrystallisation (absolute ethanol) yielded a yellowpowder, (1.654 g, 82%). Analysis Mass spectrum (CI) 342 [M+H]+

[0213]¹H NMR (250 Hz, CDCl3) 8.43 (2H,s), 8.40(2H,d, J=7.6 Hz), 8.00(1H,t,7.6J), 7.10 (4H,d,J=7.4 Hz), 6.99 (2H,t,J=7.4 Hz), 2.20 (12H,s)

[0214]¹³C NMR (250 Hz, CDCl3) 163.17, 154.45, 150.26, 137.32, 128.16,126.77, 124.39, 122.68, 18.31

[0215]10.2—Preparation of2.6-dialdiminepyridinebis(2,6-dimethylanil)FeCl₂

[0216] To FeCl₂ (0.127 g, 1.0 mmol) dissolved in hot, dry, n-butanol (40ml) at 80° C., a suspension of2,6-dialdiminepyridinebis(2,6-dimethylanil) (0.341 g, 1.0 mmol, 1 eq) inhot, dry, n-butanol (10 ml) was added dropwise at 80° C. The reactionmixture turned green. After stirring for 15 mins at 80° C. the mixturewas allowed to cool to room temperature and stirred for a further 12 h.The reaction solvent volume was reduced to approximately 1 ml and thereaction mixture was washed with diethyl ether (3×40 ml) to yield alight green powder (0.279 g, 60%).

[0217] Mass spectrum (FAB+) m/z: 467 [M]+, 432 [M-Cl]+

Example 11

[0218] 11.1—Preparation of 2,6-dialdiminepyridinebis(2,6-diethylanil)

[0219] To 2,6-pyridinedicarboxaldehyde (0.169 g, 1.25 mmol) prepared asdescribed in Example 10.0 above, in absolute ethanol (25 ml), was addedredistilled 2,6-diethylaniline (2.1 eq, 2.63 mmol, 0.36 ml) and glacialacetic acid (catalytic, 1 drop). The resulting mixture was refluxed (24h). Cooling and recrystalisation (absolute ethanol) yielded a yellowpowder, (0.371 g, 75%). Analysis—Mass spectrum (CI) 398 [M+H]+¹H NMR(250 Hz, CDCl₃) 8.44 (2H,s), 8.40 (2H,d,J=7.6 Hz), 8.00 (1H,t,J=7.6 Hz),7.25 (6H,M), 2.55 (8H,q,J=7.5 Hz), 1.61 (12H,t,J=7.5 Hz)

[0220] 11.2—Preparation of2.6-dialdiminepyridinebis(2.6-diethylanil)FeCa₂

[0221] To FeCl₂ (0.076 g, 0.6 mmol) dissolved in hot, dry, n-butanol (40ml) at 80° C., a suspension of2,6-dialdiminepyridinebis(2,6-diethylanil) (0.240 g, 0.6 mmol, 1 eq) inhot, dry, n-butanol (10 ml) was added dropwise at 80° C. The reactionmixture turned dark green. After stirring for 15 mins at 80° C. themixture was allowed to cool to room temperature and stirred for afurther 12 h. The reaction solvent volume was reduced to approximately 1ml and the reaction mixture was washed with diethyl ether (3×40 ml), toyield a dark green powder, (0.238 g,76%).

[0222] Analysis—Mass spectrum (FAB+) m/z: 523 [M]+, 488 [M-Cl]+, 453[M-Cl2]+, 398 [M-FeCl2]+

Example 12

[0223] 12.1—Preparation of2.6-dialdiminepyridinebis(2.6-diisopropylanil)

[0224] To 2,6-pyridinedicarboxaldehyde (0.101 g, 0.75 mmol)) prepared asdescribed in Example 10.0 above, in absolute ethanol (20 ml), was addedredistilled 2,6-diisopropylaniline (2.1 eq, 1.57 mmol, 0.26 ml) andglacial acetic acid (catalytic, 1 drop). The resulting mixture wasrefluxed (24 h). Cooling and recrystallisation (absolute ethanol)yielded a yellow powder, (0.270 g, 80%). Analysis—Mass spectrum (CI) 454[M+H)+

[0225]¹H NMR (250 Hz, CDCl₃) 8.44 (2H,s), 8.40 (2H,d,J=7.6 Hz), 8.00(1H,t,J=7.6 Hz), 7.23 (6H,M), 3.01 (4H,sept.,J=6.9 Hz), 1.21(24H,d,J=6.9 Hz)

[0226]¹³C NMR(250 Hz, CDCl3) 163.52, 162.69, 154.43, 148.30, 137.36,137.14, 123.05, 122.76, 27.99, 23.44.

[0227] 12.2—Preparation of2.6-dialdiminepyridinebis(2.6-diisopropylanil)FeCl₂

[0228] To FeCl₂ (0.070 g, 0.55 mmol) dissolved in hot, dry, in-butanol(40 ml) at 80° C., a suspension of2,6-dialdiminepyridinebis(2,6-diisopropylanil) (0.245 g, 0.55 mmol, 1eq) in hot, dry, n-butanol (10 ml) was added dropwise at 80° C. Thereaction mixture turned dark green. After stirring for 15 mins at 80° C.the mixture was allowed to cool to room temperature and stirred for afurther 12 h. The reaction solvent volume was reduced to approximately 1ml and the reaction mixture was washed with diethyl ether (3×40 ml), toyield a dark green powder, (0.205 g,65%).

[0229] Analysis—Mass spectrum (FAB+) m/z: 576 [M]+, 544 [M-Cl]+, 454[M-FeCl₂]+

Example 13

[0230] 13.1—Preparation of 2.6-dialdiminepyridinebis(1-naphthil)

[0231] To 2,6-pyridinedicarboxaldehyde (0.658 g, 4.81 mmol)) prepared asdescribed in Example 10.0 above, in absolute ethanol (40 ml), was added1-aminonaphthalene (2.1 eq, 10.10 mmol, 1.448 g) and glacial acetic acid(catalytic, 1 drop). The resulting mixture was refluxed (24 h). Coolingand recrystallisation (absolute ethanol) yielded a yellow powder, (1.48g, 80%). Analysis—Mass spectrum (EI) 385 [M]+

[0232] 13.2—Preparation of 2.6-dialdiminepyridinebis(1-naphthil)FeCl₂

[0233] To FeCl₂ (0.20 g, 1.57 mmol) dissolved in hot, dry n-butanol (80ml) at 80° C., a suspension 2,6-dialdiminepyridinebis(1-naphthil) (0.610g, 1.57 mmol, 1 eq) in hot, dry, n-butanol (25 ml) was added dropwise at80° C. The reaction mixture turned green. After stirring for 15 mins at80° C. the mixture was allowed to cool to room temperature and stirredfor a further 12 h. The reaction solvent volume was reduced toapproximately 1 ml and the reaction mixture was washed, with diethylether (3×40 ml) to yield a green powder, (0.57 g,71%). Analysis—Massspectrum (FAB+) m/z: 511 [M]+, 476 [M-Cl]+, 441 [M-Cl₂]+, 386 [M-FeCl₂]+

Examples 10 to 13 Polymerisation Tests

[0234] The iron complexes prepared in Examples 10 to 13 were tested inpolymerisation of ethylene under the following standard conditions. Tothe iron complex (0.01 mmol), dissolved in toluene (40 ml, dry) in aSchlenk tube, the cocatalyst (methylaluminoxane—‘MAO’) was added (0.065ml, 10 wt % in toluene, 100 eq (Fe:Al=1:100)) to produce an orangesolution. The Schlenk tube was placed in a water bath, purged withethylene and the contents magnetically stirred and maintained under 1bar ethylene for the duration of the polymerisation. After 30 minutesthe polymerisation was terminated by the addition of aqueous hydrogenchloride. The insoluble, solid, polyethylene was recovered byfiltration, washed with methanol (50 ml) and dried (vacuum oven at 50°C.). The toluene solution was dried over MgSO4, and the solvent removedunder vacuum to yield traces of waxy material. GC-MS of the toluenesolution showed the waxy material to consist of α-olefins (vinylterminated oligomeric hydrocarbons). The results of the polymerisationtests are shown in the following Table. TABLE Iron complex Soluble MWActivity/ Example Cocatalyst/ Solid PE solid g mmol⁻1 No. eq (note 1)PE/g (note 2) PE bar⁻1h⁻1 10 MAO 3.618 0.085 15000 740 11 MAO 2.9840.261 649 12 MAO 4.803 0.038 33000 968 13 MAO 0.450 0.601 900 210

[0235] Notes on the Table

[0236] 1) MAO obtained from the Aldrich Chemical Co

[0237] 2) Recovered from the reaction medium. In Example 13 the Mw ofthe soluble PE (polyethylene) was 300.

Examples 14 to 25

[0238] These Examples are a series of tests wherein ethylene orethylene/l-hexene is polymerised under 10 bars ethylene pressure usingthe catalysts of the present invention under “slurry” polymerisationconditions.

[0239] Catalyst Preparation

[0240] The transition metal complexes employed as catalyst in Examples14 to 25 were as follows:

[0241] In Examples 14 and IS the complex was2,6-diacetylpyridinebis(2,6-didsopropylanil)FeCl₂ prepared as describedin Example 1 (Formula D compound).

[0242] In Examples 16 to 20 the complex was was2,6-diacetylpyridinebis(2,6-dimethylanil)FeCl₂ prepared as described inExample 8.

[0243] In Example 21 the complex was2,6-diacetylpyridinebis(2,4-dimethylanil)FeCl₂ prepared as described inExample 7.

[0244] In Examples 22 to 24 the complex was2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ prepared as describedin Example 9.

[0245] In Example 25 the complex was2,6-diacetylpyridinebis(2,6-diisopropylanil)CoCl₂ prepared as describedin Example 3 (Formula K).

[0246] Catalyst Activation

[0247] The transition metal complex was dissolved in toluene (previouslydried over sodium metal) under a nitrogen atmosphere and there was addeda solution of activator (cocatalyst) at ambient temperature. The mixturewas stirred at room temperature then an aliquot transferred to theinjection unit of a polymerisation reactor. The quantities of reagentsemployed in the catalyst activation are set out in the following Table.All operations were conducted under a nitrogen atmosphere unlessspecified. “MAO” is

[0248] methyl aluminoxane (1.78M in toluene supplied by Witco). “MMAO”is modified methyl aluminoxane (10%w/w in heptane—supplied by Witco)were used as purchased. Triisobutylaluminium (Al(iBu)₃ as a 1M solutionin toluene was supplied by Aldrich. TABLE Metal Solution Complex [Metal]Cocatalyst [Al] Toluene Molarity Ex. No. (mg) (μmols) type (ml) mmols[M]:[Al] (ml) (M) 14 3 5 MAO 2.78 5 1:1000 20 0.0025 15 3 5 MAO 2.78 51:1000 20 0.0025 16 1.5 3 MAO 1.70 3 1:1000 10 0.0025 17 1.5 3 MMAO 3.933 1:1000 10 0.0025 18 1.5 3 MAO 1.70 3 1:1000 50 0.0006 19 1.5 3 MAO1.70 3 1:1000 10 0.0025 20 1.5 3 MAO 0.17 3 1:1000 10 0.0025 21 1.5 3MAO 1.70 3 1:1000 10 0.0025 22 3 6 MAO 3.22 6 1:1000 20 0.003 23 1.5 3MAO 1.61 3 1:1000 10 0.003 24 3 6 MAO 0.32 0.3 1:100 20 0.003 25 3 5 MAO2.78 5 1:1000 20 0.0025

[0249] Polymerisation Tests

[0250] The reagents used in the polymerisation tests were Ethylene Grade3.5 (supplied by Air Products), hexene (supplied by Aldrich) distilledover sodium/nitrogen and triisobutylaluminium (1M in hexanes, suppliedby Aldrich).

[0251] Polymerisation of Ethylene

[0252] A 1 liter reactor was baked out under a nitrogen flow for atleast 1 hour at >85° C. The reactor was then cooled to 50° C. Isobutane(0.5 liter) and triisobutylaluminium were then added and the reactor wasboxed in nitrogen. The alkyl aluminium was allowed to scavenge forpoisons in the reactor for at least 1 hour. Ethylene was introduced intothe reactor until a predetermined over-pressure was achieved then thecatalyst solution was injected under nitrogen. The reactor pressure wasmaintained constant throughout the polymerisation run by computercontrolled addition of additional ethylene. The polymerisation time was1 hour. Upon termination of the run the reactor contents were isolated,washed with acidified methanol (50ml HCl/2.51 methanol) andwater/ethanol (4:1 v/v) and dried under vacuum, at 40° C., for 16 hours.

[0253] Copolymerisation of Ethylene/1-Hexene (Example 19)

[0254] A 1 liter reactor was baked out under a nitrogen flow for atleast 1 hour at >85° C. The reactor was then cooled to 50° C., isobutane(0.5 liter), 1-hexene and triisobutylaluminium were then added and thereactor was boxed in nitrogen. The alkyl aluminium was allowed toscavenge for poisons in the reactor for at least 1 hour. Ethylene wasintroduced into the reactor until a predetermined over-pressure wasachieved then the catalyst solution was injected under nitrogen. Thereactor pressure was maintained constant throughout the polymerisationrun by computer controlled addition of ethylene. The polymerisation timewas 40 minutes. Upon termination of the run the reactor contents wereisolated, washed with acidified methanol (50 ml HCV2.51 methanol) andwater/ethanol (4:1 v/v) and dried under vacuum, at 40° C., for 16 hours.

[0255] Data from the polymerisation tests are set out below in the TableTABLE metal/ polymerisation activity Ex. [metal] aluminoxane C₂H₄Al(iBu)₃ Temp. polymer (g/mmol No. (μmols) Ratio Bar (ml) (° K) (g)M/h/b) ppm 14 0.5 1:1000 10 3 323 26.9 5430 1.03 15 0.5 1:1000 10 3 29845.0 9090 0.61 16 0.6 1:1000 10 3 323 56.5 9340 0.60 17 0.6 1:1000 10 3323 57.4 9510 0.59 18 0.12 1:1000 10 3 323 3.3 2540 2.2 19# 0.6 1:100010# 3 323 67.6 16690 0.50 20 0.6 1:1000 10 3 323 74.5 12310 0.45 21 0.61:1000 10 3 323 7.8 1280 4.36 22 0.6 1:1000 10 3 323 63.1 11020 0.51 230.12 1:1000 10 3 323 55.7 48690 0.11 24 0.6 1:100  2 2 323 18.21 151501.84 25 0.8 1:1000 10 3 323 3.7 450 13.1

[0256] Notes on the Table

[0257] # Example 19 illustrated copolymerisation of ethylene with1-hexene. 1-Hexene (50 ml) was included in the polymerisation. Theremaining Examples were all homopolymerisation of ethylene.

[0258] “ppm” is defined as parts by weight of transition metal permillion parts by weight of polymer.

[0259] Molecular weight data of the polymers obtained from Examples 14to 25 are set out in the Table below. TABLE Ex. No. Mw Mn Mpeak PD 14611000 64000 246000 9.5 15 857000 212000 451000 4.0 16 242000 9600 1600025.3 17 278000 5700 1300 48.7 18 366000 50000 102000 7.3 19 377000 650043000 57.7 21 470 360 370 1.3 25 14000 4200 12000 3.3

Examples 26 and 27

[0260] Gas Phase Polymerisation Tests with Supported Catalysts

[0261] Examples 26 and 27 illustrate the use of the catalysts of thepresent invention supported on silica support material. Example 26employs 2,6-diacetylpyridinebis(2,6-disopropylanil)FeCl₂, and Example 27employs 2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ as thetransition metal complex compound.

Example 26

[0262] Preparation of the Supported Catalyst

[0263] 2,6-Diacetylpyridinebis(2,6-diisopropylanil)FeCl₂ was prepared asdescribed in Example 1.

[0264] Silica (1.03 g ES70, supplied by Crosfield), which had beenheated under flowing nitrogen at 700° C., was placed in a Schlenk tube,and toluene (10 ml) was added. The mixture was heated to 50° C. To asolution of 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl₂ (0.036 g)in toluene (10 ml) was added methylaluminoxane (5 ml, 1.78M in toluene,supplied by Witco). This mixture was heated at 50° C. and thentransferred to the silicattoluene mixture. The silica/MAO/toluenemixture was maintained at 50° C., with regular stirring, for 1 hourbefore the toluene was removed, at 65° C., under vacuum to yield a freeflowing powder.

Example 27

[0265] Preparation of the Supported Catalyst

[0266] 2,6-Diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ was prepared asdescribed in Example 9. Silica (1.38 g ES70, supplied by Crosfield),which had been heated under flowing nitrogen at 700° C., was placed in aSchlenk tube and toluene (10 ml) was added.

[0267] To a solution of2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ (0.041 g) in toluene(10 ml) was added methylaluminoxane (13.2 m], 1.78M in toluene, suppliedby Witco). This mixture was heated at 40° C. for 30 minutes to dissolveas much of the iron complex as possible. The solution was thentransferred to the silica/toluene. The silica/MAO/toluene mixture wasmaintained at 40° C., with regular stirring, for 30 minutes before thetoluene was removed, at 40° C., under vacuum to yield a free flowingpowder. Analysis of the solid gave 16.9%w/w Al and 0.144%w/w Fe.

[0268] Polymerisation Tests—Examples 26 and 27

[0269] The reagents used in the polymerisation tests were hydrogen Grade6.0 (supplied by Air Products): ethylene Grade 3.5 (supplied by AirProducts): hexene (supplied by Aldrich) distilled over sodium/nitrogen:dried pentane (supplied by Aldrich): methylaluminium (2M in hexanes,supplied by Aldrich): and triisobutylaluminium (1M in hexanes, suppliedby Aldrich).

[0270] A 3 liter reactor was baked out under flowing nitrogen for atleast 1 hour at 77-85° C. before powdered sodium chloride (300 g,predried under vacuum, 160° C., >4 hours) was added. The sodium chloridewas used as a fluidisablelstirrable start-up charge powder for the gasphase polymerisation. Trimethyl aluminium (3 ml, 2M in hexanes) wasadded to the reactor and was boxed in nitrogen. The alkyl aluminium wasallowed to scavenge for poisons in the reactor for between ½-1 hourbefore being vented using 4×4 bar nitrogen purges. The gas phasecomposition to be used for the polymerisation was introduced into thereactor and preheated to 77° C. prior to injection of the catalystcomposition. The catalyst (0.18-0.22 g) was injected under nitrogen andthe temperature then adjusted to 80° C. The ratio of hexene and/orhydrogen to ethylene during the polymerisation was kept constant bymonitoring the gas phase composition by mass spectrometer and adjustingthe balance as required. The polymerisation tests were allowed tocontinue for between 1 to 2 hours before being terminated by purging thereactants from the reactor with nitrogen and reducing the temperature to<30° C. The produced polymer was washed with water to remove the sodiumchloride, then with acidified methanol (50 ml HCl/2.5 L methanol) andfinally with water/ethanol (4:1 v/v). The polymer was dried undervacuum, at 40° C., for 16 hours. Several Runs, using a variety ofoperating conditions were carried out with each of the catalysts ofExamples 26 and 27. All the polymerisation tests were carried out at apolymerisation temperature of 80° C. and at an ethylene pressure of 8bars. The polymerisation conditions are set out in the following TableTABLE MAO/ other co- Run Activity Metal Metal catalyst/ H₂ hexenepentane time g/mmol Ex/Run (% w/w) Ratio (mmols) (bar) (bar) (bar) (min)M/h/b 26.1 0.21 150 **** **** **** **** 75 77 26.2 0.21 150 **** ****0.195 **** 90 77 26.3 0.21 150 TMA /6 **** **** **** 60 149 26.4 0.21150 TMA /6 0.75 **** **** 60 318 27.1 0.144 300 **** **** **** **** 60611 27.2 0.144 300 TMA /6 0.5 **** **** 60 832 27.3 0.144 300 TMA /6 0.50.2 **** 60 1054 27.4 0.144 300 TMA /6 0.5 **** 2.4 60 1800 27.5 0.144300 TiBA /3  **** **** **** 60 713 27.6 0.144 300 **** 3 **** **** 60501 27.7 0.144 300 **** **** 0.86 **** 60 418

[0271] Molecular weight data on the polymer products is set out in theTable below. Run Catalyst Mw Mn Mpeak Polydispersity 26.2 Ex 26 892000106000 332000 8.4 26.3 Ex 26 278000 8400 95000 33.0 26.4 Ex 26 1950007200 43000 27.0 27.1 Ex 27 324000 9300 134000 34.6 27.2 Ex 27 22300018000 42000 12.3 27.3 Ex 27 77000 6000 21000 12.8 27.4 Ex 27 154000 570028000 26.9 27.5 Ex 27 207000 4800 86000 43.1 27.6 Ex 27 69000 5400 1400012.7 27.7 Ex 27 127000 14000 51000 9.3

[0272] The polymer obtained in Example 27.7 contained short chainbranching (SCB) corresponding to 1.6 n-butyl branches/1000 C.

Example 28

[0273] 28,0—Preparation of2,6-dialdiminepyridinebis(2.4.6-trimethylanil)

[0274] 2,6-dimethanolpyridine (6.53 g, 0.048 mol) in absolute ethanol(50 ml), 2,4,6-trimethylaniline (2.5 equivalents, 17.0 ml, 0.12 mol) andglacial acetic acid (3 drops) were mixed together and refluxed for 24hours. On cooling the mixture, yellow crystals of2,6-dialdiminepyridinebis(2,4,6-trimethylanil) were separated out (14.28g, 80% yield).

[0275] Analysis of the crystalline product by ¹H NMR: (250 Hz) 8.42(s,2H), 8.40 (s, 2H), 8.0(t,³J(HH) 8, JH), 7.0(s, 4H), 2.33(s, 6H), 2.19(s,12H).

[0276] Mass spectrum: m/z 369 [M]⁺.

[0277] 28.1—Preparation of2,6-dialdiminepyridinebis(2,4,6-trimethylanil)FeCl₃ (Formula G)—SeeBelow

[0278] FeCl₃ (0.10 g; 0.615 mmol) was dissolved in MeCN (25 ml) at roomtemperature and 2,6-dialdiminepyridinebis(2,4,6-trimethylanil) (0.227 g,0.615 mmol) added. After 24 hours stirring at room temperature a redprecipitate of 2,6-dialdiminepyridinebis(2,4,6-trimethylanil)FeCl₃(0.192 g, 60%) was collected and dried. Analysis of the product: Massspectrum: m/z 531 [M]⁺, 496 [M-Cl]⁺, 462[M-2Cl]⁺.

[0279] 28.2—Polymerisation Test

[0280] The 2,6-dialdiminepyridinebis(2,4,6-trimethylanil)FeCl₃ (0.02mmol) prepared as above was dissolved in toluene (40 ml) in a Schlencktube, to give a red solution and the cocatalyst (methylalumoxane), MAO)(8,0 mmol, 400 equiv.) introduced (formation of a orange solution wasobserved). The MAO was supplied by Aldrich (catalogue number: 40,459-4).The tube was purged with ethylene and the contents stirred under 1 barethylene for the duration of the polymerisation. The run was stoppedafter 0.5 hour by adding aqueous HCl solution. Solid polyethylene (1.5g) was collected by filtration, washed with methanol and dried in avacuum oven at 50° C. Polyethylene soluble in the toluene was isolatedfrom the filtrate by separation of the toluene layer from the aqueouslayer, drying over MgSO₄ and removal of the toluene by distillation. Theweight of toluene-soluble polyethylene obtained was 2.46 g. The catalystactivity (based on the total weight of polyethylene obtained) was 396 gmmol⁻¹ h⁻¹ bar⁻¹.

Example 29

[0281] Preparation of a Catalyst from2.6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂

[0282] 2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ prepared asdescribed in Example 9. To2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ (17 mg, 0.03 mmol)dissolved in Et₂O (20 ml), at −78° C., was added dropwise a solution oftrimethylsilylmethyl magnesium chloride(0. 164 mmol, 1M solution inEt₂O). The solution was stirred for 10 minutes then allowed to warm to0° C. and stir for a further 5 minutes. The reaction solvent was removedunder reduced pressure. To the iron complex was addedtrityltetratpentafluorophenyl)borate(151 mg, 0.164 mmol) and toluene (20ml, dried) yielding a red solution. The Schlenk tube was purged withethylene and the contents magnetically stirred and maintained under 1bar ethylene for the duration of the polymerisation. After 60 minutesthe polymerisation was terminated by addition of acidified methanol (50ml HCl/2.5 L methanol). The insoluable, solid, polyethylene wasrecovered by filtration, washed with methanol/water (1:4 v/v) and dried(vacuum oven at 40° C.). Yield of solid polyethylene 0.90 g, apolymerisation activity of 28 gmmol⁻¹bar⁻¹h⁻¹.

[0283] Reagents used in Example 29 were as follows:

[0284] Trimethylsilylmethyl magnesium chloride(purchased from Aldrich asa 1M solution in Et₂O)

[0285] Trityltetra(pentafluorophenyl)borate (purchased from Boulder)

[0286] Diethylether (purchased from Aldrich, dried over sodium)Toluene(purchased from Aldrich, dried over sodium)

Examples 30 and 31

[0287] In these Examples, iron (II) complexes comprising tridentatepyridine-hydrazone ligands in accordance with the present invention weresynthesised and tested as olefin polymerisation catalysts.

[0288] 30.1—Preparation of 2,6-bis(1-methyl, 1-phenylhydrazone)pyridine

[0289] 2,6-diacetylpyridine (5.0 g, 30.6 mmol) [Aldrich Chemicals] and1-methyl,1-phenylhydrazine (7.21 ml, 61.3 mmol) [Aldrich Chemicals] inabsolute ethanol were stirred together and then heated to reflux for 12hours. On reducing the volume of the solution by evaporating some of theethanol and cooling to −20° C., yellow needles of 2,6-bis(1-methyl,1-phenylhydrazone)pyridine were obtained which were filtered off. Yieldca 90%. Mass spectrum:m/z. M⁺372. Analysis by ¹H NMR (300 MHz, CDCl₃,298K)δ:2.52 (s, 6H, CH₃C═N), 3.32 (s, 6H, CH₃-N), 6.95-8.31 (multiplets,13H, aryls).

[0290] 30.2—Preparation of 2.6-bis(1-methyl,1-phenylhydrazone)pyridine.FeCl₂ Complex

[0291] FeCl₂.4H₂O (0.21 g; 1.06 mmol) and 2,6-bis(1-methyl,1-phenylhydrazone)pyridine (0.39 g; 1.06 mmol) were stirred together inanhydrous n-butanol (10 ml) and heated at 80° C. for 2 hours. Thereaction was then allowed to cool down to room temperature. Removal ofvolatiles in-vacuo, extraction into warm MeCN (30 ml) and cooling (−20°C.) afforded the desired iron complex (Formula L below) as large brownneedles. Yield ca 85%.

[0292] 31.1—Preparation of 2,6-bis(1,1-diphenylhydrazone)pyridine

[0293] This compound was prepared in analogous manner to that outlinedin Example 30.1 using 2,6-diacetylpyridine (1.0 g, 6.13 mol) and1,1-diphenylhydrazine hydrochloride (2.7 g, 12.3 mmol) [AldrichChemicals]. Yield ca 85%. Analysis by

[0294]¹H NMR (300 MHZ, CDCl₃, 298K)δ:2.12 (s, 6H, CH₃C═N), 7.09-8.35(multiplets, 23E, aryls).

[0295] 31.2—Preparation of 2,6-bis(1,1-diphenylhydrazone)pyridine.FeCl₂Complex

[0296] This complex (see Formula M below) was prepared by an analogousmanner to that outlined in Example 30.2 from FeCl₂.4H₂O (0.5 g, 2.51mmol) and 2,6-bis(1,1-diphenylhydrazone)pyridine (1.19 g, 2.52 mmol).Yield ca 70%

[0297] Mass spectrum:m/z M⁺-Cl 586.

[0298] 30.3 and 30.4—Polymerisation Tests

[0299] The iron complexes prepared in Examples 30.2 and 31.2 were testedin polymerisation of ethylene under the following standard conditions.To the iron complex, dissolved in toluene (40 ml, dried over sodiumwire) in a Schlenk tube, the cocatalyst (methylaluminoxane—“MAO”) wasadded. The “MAO” was purchased from Witco as a 1.78M solution intoluene. The Schlenk tube was purged with ethylene and the contentsmagnetically stirred and maintained under 1 bar ethylene for theduration of the polymerisation. After 60 minutes the polymerisation wasterminated by addition of acidified methanol (50 ml HCl/2.5 litersmethanol). The insoluble, solid, polyethylene was recovered byfiltration, washed with methanol/water (1:4 v/v) and dried (vacuum ovenat 50° C.). For Example 30, the produced polyethylene solution was driedover MgSO₄ and the solvent removed under vacuum to yield traces of awaxy material. The results of the polymerisation tests are shown in thefollowing Table TABLE Activity/ Catalyst/ Cocatalyst/ Fe:Al Solid Sol.gmmol⁻¹ EX. mmol mmol Ratio PE/g PE bar⁻¹h⁻¹ 30 0.02 8 1:400 — 0.04  231 0.008 3.2 1:400 1.01 — 130

[0300]

Example 32

[0301] 32.1—Preparation of a Supported Ziegler Catalyst Component

[0302] Silica (20 kg), grade ES 70 supplied by Crosfield, which had beendried at 800° C. for 5 hours in flowing nitrogen, was slurried in hexane(110 liters) and hexamethyldisilazane (30 moles), supplied by Fluka, wasadded with stirring at 50° C. Dry hexane (120 liters) was added withstirring, the solid allowed to settle, the supernatant liquid removed bydecantation and further dry hexane (130 liters) was added with stirring.The hexane washing was repeated a further 3 times. Dibutylmagnesium (30moles), supplied by FMC, was added and stirred for 1 hour at 50° C.Tertiary butyl chloride (60 moles) was added and stirred for 1 hour at50° C. To this slurry was added an equimolar mixture of titaniumtetrachloride (3 moles), and titanium tetra-n-propoxide (3 moles) withstirring at 50° C. for 2 hours, followed by 5 washings with dry hexane(130 liters). The slurry was dried under a flowing nitrogen stream togive a solid, silica supported Ziegler catalyst component.

[0303] 32.2—Preparation of a Mixed Catalyst Containing a ZieglerComponent and a Transition Metal Compound of the Present Invention

[0304] A solution of methylaluminoxane (“MAO”, 10.2 mmol) as a 10% wtsolution in toluene, supplied by Witco, was added to a suspension of2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂ (0.07 mmol in 5 ml drytoluene), prepared as in Example 9, and the mixture shaken for 5minutes. This solution was then added to 2.0 g of the silica supportedZiegler catalyst prepared above (Example 32. 1), the mixture shaken for2 hours at 20° C. and then the solvent removed under reduced pressure at20° C. to yield the mixed catalyst as a free flowing powder.

[0305] 32.3—Polymerisation of Ethylene/Hexene Mixture Using the MixedCatalyst

[0306] A 3 liter reactor equipped with a helical stirrer was heated to95° C. for 1 hour with dry nitrogen flowing through. The temperature wasreduced to 50° C. and dry sodium chloride (300 g) was then added withtrimethylaluminium (TMA) solution (2 ml of 2 molar ThA in hexane) andthe reactor heated at 85° C. for 2 hours. The reactor was purged withnitrogen, cooled to 50° C. and TMA solution (3 ml of 2 molar TMA inhexane) added. The temperature was raised to 77° C. and hydrogen (0.5bar) and ethylene (8 bar) added prior to the addition of 1-hexene (2.6ml). Reaction was started by injection into the reactor of the mixedcatalyst (0.20 g) prepared above. The temperature was maintained at 80°C. and ethylene added to maintain constant pressure. The gas phase wasmonitored by a mass spectrometer and hydrogen and 1-hexene added asnecessary to maintain constant gas phase concentrations of thesecomponents. The polymerisation was carried out for 90 minutes. Thepolymer was washed with water to remove the sodium chloride, then withacidified methanol (50 ml HCl/2,5 liters methanol) and finally withwater/ethanol (4:1 v/v ). The polymer was dried under vacuum, at 40° C.for 16 hours. 111 g of dried polymer was produced. The polymer had abroad molecular weight distribution (as determined by gel permeationchromatography. The polydispersity (Mw/Mn) was 28.5.

Example 33

[0307] 33.1—Pre-Impregnation of Support with Activator Compound

[0308] All the following operations were conducted under a nitrogenatmosphere unless stated. Silica (Crosfield grade ES70X) was heatedunder flowing nitrogen at 250° for 16 hours. A sample of this silica(2.5 g) was placed in a Schlenk tube and had 12.1 ml of 1.78Mmethylaluminoxane, MAO (supplied by Witco) added to it to form a slurry.The slurry was heated for 4 hours at 50° C. before being left for 10days at room temperature. The supernatant liquid above the silica wasremoved and the silica/MAO washed three times with toluene (3×10 ml) atroom temperature, removing the supernatant solution each time.

[0309] 33.2—Supporting the Catalyst

[0310] (2,6-diacetylpyridinebis(2,4,6 trimethyl anil) iron dichloride(0.101 g) (prepared as described in Example 9) was slurried in toluene(20 ml), at room temperature, and added to the silica/MAO. The mixturewas occasionally shaken over a 1 hour period. The supernatant solutionwas removed and the silica/MAO/Fe complex was washed with toluene untilthe filtrate was colourless. The solid was dried under vacuum at 50° C.

[0311] 33.3—Gas Phase Polymerisation of Ethylene

[0312] A 3 liter reactor was baked out under flowing nitrogen for atleast 1 hour at 77° C. before sodium chloride (300 g, <1 mm diameterparticles, predried under vacuum, 160° C., >4 hours) was added. Thesodium chloride was employed merely as a standard “charge powder” forthe gas phase polymerisation reactor. Trimethyl aluminium (3 ml, 2M inhexanes, supplied by Aldrich) was added to the reactor which was thenclosed. The alkyl aluminium was allowed to scavenge for poisons in thereactor for 12 hour before being vented by successive pressurising andpurging the reactor with 4 bar of nitrogen. Ethylene (Grade 3.5,supplied by Air Products) was added to the reactor to give a pressure of8 bar, at 77° C., prior to catalyst injection. The supported catalyst(0.215 g) prepared as described in Example 33.2 was injected into thereactor under nitrogen and the temperature then adjusted to 80° C. Thepolymerisation was allowed to continue for 5 hours before beingterminated by purging the ethylene from the reactor, using nitrogen, andreducing the temperature to below 30° C. The polymer was washed withwater to remove the sodium chloride, then with acidified methanol (50 mlHCl/2.5 liters methanol) and finally with water/ethanol (4:1 v/v). Thepolymer was dried under vacuum, at 40° C., for 16 hours. 161 g of driedpolymer was produced.

Example 34 Polymerisation Catalyst Modified with a Neutral Lewis Base

[0313] The 2,6-diacetylpyridinebis(2,6-diisopropylanil)FeCl₂ complexprepared in Example 1 was tested in polymerisation of ethylene under thefollowing standard conditions. To the iron complex (8 μmol) dissolved indried toluene (10 ml) in a Schlenk tube, a solution ofN,N-dimethylaniline in toluene (10 ml) then the cocatalyst(methylaluminoxane—‘MAO’, 8 mmol of a 1.78 M MAO solution in toluene,supplied by Witco, reference AL 5100/10T) was added. The contents of theSchlenk were magnetically stirred and maintained under 1 bar ethylenefor the duration of the polymerisation. After 60 minutes the producedpolymer was washed with acidified methanol (50 ml HCl/2.5 litersmethanol) and finally with water/ethanol (4:1 v/v). The polymer wasdried under reduced pressure, at 40° C., for 16 hours. Several runs,using a variety of operating conditions were carried out and thepolymerisation conditions are set out in the following Table. DMA Fe/DMARun μmol Ratio Activity Mw Mn Mw/Mn 34.1  8  1 890 790 660 1.2 34.2  80 10 617 1000 720 1.4 34.3 800 100 892 63000 4825 20.7 C — — 1030 890001100 77.8

[0314] Notes on the Table

[0315] DMA is N,N-dimethylaniline

[0316] Activity is expressed as g polymer mmol⁻¹ transition metalh⁻¹bar⁻¹

[0317] C=Comparative Test using no DMA

Examples 35 to 38

[0318] These illustrate the preparation of supported catalysts inaccordance with the present invention and their use in thepolymerisation of ethylene under “slurry” polymerisation conditions.

Example 35

[0319] 35.1—Preparation of 2,6-diacetylpyridinebis(2,4,6 Trimethyl Anil)Iron Dichloride Supported on MAO/Silica

[0320] Silica support material (grade ES70X supplied by Crosfield) washeated under flowing nitrogen at 250° C. for 16 hours. A sample of thissilica was placed in a Schlenk tube and 12.1 ml of 1.78Mmethylaluminoxane (“MAO” supplied by Witco) was added to it to form aslurry. The slurry was heated for 4 hours at 50° C. before being leftfor 10 days at room temperature. The supernatant liquid above the silicawas then removed and the silica/MAO washed 3 times with toluene (10 ml)at room temperature, removing the supernatant solution each time.2,6-diacetylpyridinebis(2,4,6 trimethyl anil) iron dichloride complex(0.101 g) was slurried in toluene (20 ml), at room temperature, andadded to the silica./MAO. The mixture was occasionally shaken over a 1hour period. The supernatant solution was removed and the producedsilica-supported MAO/Fe complex washed with toluene until the initialwashings, which were light orange in colour, became clear and free fromcolour. The produced silica-supported catalyst solid was dried undervacuum at 50° C.

[0321] 35.2—Polymerisation of Ethylene

[0322] A 1 liter reactor was heated under flowing nitrogen (2liters/min) for 1 hour at 95° C. The reactor was cooled to 40° C. and500 ml of isobutane added. The temperature of the reactor was raised to80° C. and ethylene admitted to the reactor to give a partial pressureof 10 bar. The supported catalyst prepared in 35.1 above (0.201 g,slurried in 10 ml of toluene) was injected under nitrogen and thepressure increase in the reactor taken into account during control ofthe reactor pressure during the polymerisation test. The test wasterminated after 1 hour and the polymer dried under vacuum at 40° C. 5.9g of polymer was recovered. Analysis of the polymer by GPC indicated Mwand Mn to be 124000 and 15000 respectively.

[0323] 35.3—Polymerisation of Ethylene

[0324] A 1 liter reactor was heated under flowing nitrogen for 3 hoursat 80° C. The reactor was cooled to less than 30° C. and 500 ml ofisobutane added. Trimethyl aluminium (3 ml of 2M in hexanes) was addedto the reactor and this was then heated to 80° C. The pressure in thereactor increased to 13.8 bar and then ethylene was admitted to give atotal pressure of 23.8 bar. The supported catalyst prepared in 35.1above (0.201 g of the supported catalyst solid in toluene slurry) wasinjected into the reactor under nitrogen causing the reactor pressure toincrease to 25.4 bar. The catalyst activity was slightly too high forthe ethylene inlet flow to keep the pressure constant and this wastherefore allowed to fall to 23.2 bar. The ethylene pressure present inthe reactor for the majority of the polymerisation was estimated to be7.8 bar. The test was terminated after 1.75 hours and the polymer washedwith methanol/HCl (2.5 liters/50 ml), then water/ethanol (4:1 v/v) anddried under vacuum at 40° C. 166 g of dry polymer was recovered.Analysis of the polymer by GPC indicated Mw and Mn to be 182000 and11000 respectively.

Example 36

[0325] 36.1—Preparation of 2.6-diacetylpyridinebis(2,4,6 Trimethyl Anil)Iron Dichloride Supported on MAO/Silica

[0326] A portion (about 1-1.5 g) of the supported catalyst prepared inExample 35.1 was washed with 5×10 ml aliquots of toluene at 100° C. Theinitial washings had a deep orange colour and this coloration becameless with each subsequent washing until the final washing was clear ofcolour. The solid was dried under vacuum at 100° C. to providefree-flowing solid supported catalyst.

[0327] 36.2—Polymerisation of Ethylene

[0328] A 1 liter reactor was heated under flowing nitrogen for 1 hour at75° C. Trimethyl aluminium (3 ml of 2M in hexanes) was added to thereactor which was then cooled to 50° C. Isobutane (500 ml) was added tothe reactor and the temperature increased to 76° C. The pressure in thereactor increased to 13 bar. Ethylene was admitted to the reactor togive 21 bar total pressure (8 bar ethylene). The supported catalystprepared in 26.1 above (0.11 g in toluene slurry) was injected into thereactor and the pressure increase taken into account during control ofthe reactor pressure during the test. The temperature was increased to80° C. After 1 hour a further aliquot of the same catalyst was injected(0.22 g in hexane slurry) and the test continued for a further 3.5hours. 25 g of polymer was recovered. Analysis of the polymer by GPCindicated Mw and Mn to be 343000 and 35000 respectively.

Example 37

[0329] 37.1—Preparation of 2,6-diacetylpyridinebis(2,4,6 Trimethyl Anil)Iron Dichloride Supported on MAO/Silica

[0330] Methyl aluminoxane (24 ml of 1.78M in toluene, supplied by Witco)was added to silica (5 g of grade ES70X supplied by Crosfield) which hadbeen heated under flowing nitrogen at 250° C. The silica/MAO was heatedat 80° C. for 1 hour before being washed toluene (5×10 ml aliquots).Half of the produced silica/MAO slurry, cooled to room temperature, wasused for the next stage of the catalyst preparation (the other half wasput aside for use in Example 38). 2,6-Diacetylpyridinebis(2,4,6trimethyl anil) iron dichloride (73 mg) was slurried in toluene andtransferred to the half-portion of silia/MAO/toluene and left to reactfor 2 hours with occasional mixing. The silica/MAO/Fe complex was washedwith toluene (3×10 ml aliquots) at room temperature and then with hexane(2×10 ml aliquots) at room temperature to remove the toluene beforefinally being washed with hexane at 80° C. (3×10 ml aliquots). Theproduced supported catalyst solid was dried under vacuum at roomtemperature. The solid contained 0.107 weight % Fe.

[0331] 37.2—Polymerisation of Ethylene

[0332] A 1 liter reactor was heated under flowing nitrogen for 1 hour at80° C. The reactor was cooled to less than 30° C. and 500 ml ofisobutane added. The reactor was heated to 77° C. and the pressureincreased to 13.8 bar. Ethylene was added to give 21.8 bar totalpressure (8 bar ethylene). Triisobutyl aluminium (5 ml of 1M in hexanes)was added to the reactor and after 20 minutes the supported catalystprepared in 37.1 above (0.14 g in hexane slurry) was injected into thereactor and the pressure increase taken into account during control ofthe reactor pressure during the test. The temperature was increased to80° C. After 5 hours the polymerisation was terminated. 138 g of polymerwas recovered. Analysis of the polymer by GPC indicated Mw and Mn to be567000 and 53000 respectively. The produced polymer contained 1.02 ppmof Fe arising from the catalyst.

[0333] 37.3—Polymerisation of Ethylene

[0334] A 1 liter reactor was heated under flowing nitrogen for 1 hour at78° C. The reactor was cooled to less than 30° C. and 500 ml ofisobutane added. Triisobutyl aluminium (3 ml of IM in hexanes) was addedto the reactor which was then heated to 78° C. and the pressureincreased to 12.1 bar. Ethylene was added to give 32.0 bar totalpressure (19.9 bar ethylene). The supported catalyst prepared in 37.1above (0.0925 g, slurried in hexane) was injected into the reactor andthe total pressure was controlled at 31.2 bar. The ethylene pressureduring the polymerisation was estimated to be approximately 19.1 bar.Polymerisation was allowed to continue for 80 minutes. 18 Ig of polymerwas recovered. Analysis of the polymer by GPC indicated Mw and Mn to be595000 and 44000 respectively. The polymer contained 0.51 ppm of Fearising from the catalyst.

[0335] 37.4—Polymerisation of Ethylene

[0336] A 1 liter reactor was heated under flowing nitrogen for 1 hour at80° C. before being cooled to less than 30° C. Triisobutyl aluminium (3ml of IM in hexanes) was added to the reactor followed by 500 ml ofisobutane. The reactor was heated to 78° C. and the pressure increasedto 13.5 bar. Ethylene was added to give 17.6 bar total pressure (4.1 barethylene). The supported catalyst prepared in 37.1 above (0.15 g,slurried in hexane) was injected into the reactor. The ethylene pressureduring the polymerisation was estimated to be approximately 4.7 bar.Polymerisation was allowed to continue for 80 minutes. 21 g of polymerwas recovered. Analysis of the polymer by GPC indicated Mw and Mn to be347000 and 26000 respectively.

Example 38

[0337] 38.1—Preparation of 2.6-diacetylpyridinebis(2.6 Diisopropyl Anil)Cobalt Dichloride Supported on MAO/Silica

[0338] The second half of the silica/MAO made in Example 37.1 was driedunder vacuum. An aliquot of the dried silica/MAO (1 g) was placed in toa Schlenk tube and 2,6-diacetylpyridinebis(2,6 diisopropyl anil) cobaltdichloride (40 mg) added to this as a dry powder. Hexane (10 ml) wasthen added to the Schienk tube and the cobalt complex and silica/MAOslurried together for 1 hour at room temperature. The mixture was driedunder vacuum at room temperature to leave the produced supportedcatalyst as a dry, free flowing powder.

[0339] 38.2—Polymerisation of Ethylene

[0340] A 1 liter reactor was heated under flowing nitrogen for 1 hour at80° C. before being cooled to 30° C. Hexene (250 ml), triisobutylaluminium (3 ml of IM in hexanes) and 250 ml of isobutane were added tothe reactor. The reactor was heated to 80° C. and the pressure increasedto 7.1 bar. Ethylene was added to give 19.2 bar total pressure (12.1 barethylene). The supported catalyst prepared in above (0.245 g, slurriedin hexane) was injected into the reactor and the pressure increase takeninto account during control of the reactor pressure during the test.Polymerisation was allowed to continue for 330 minutes. 3.3 g of polymerwas recovered. Analysis of the polymer by GPC indicated Mw=5300 andMn=1500.

Example 39 Polymerisation of Ethylene in Slurry Phase Using a SupportedCatalyst

[0341] A series of polymerisation tests was carried out using a catalystbased on a supported 2,6-diacetylpyridinebis(2,4,6 trimethyl anil) irondichloride.

Example 39.1

[0342] A 1 liter reactor was heated under flowing nitrogen for 1 hour at80° C. before being cooled to 30° C. Isobutane (500 ml) followed bytriisobutyl aluminium (3 ml of 1M in hexanes) was added to the reactor.The reactor was heated to 78° C. and the pressure increased to 13.2 bar.Ethylene was added to give 26.2 bar total pressure. The catalyst ofExample 37.1 (0.097 g, slurried in hexane) was injected into thereactor. The reactor pressure was controlled at 26.0 bar during the test(ethylene pressure estimated to be approximately 12.8 bar) and thetemperature adjusted to 80° C. Polymerisation was allowed to continuefor 60 minutes. 78 g of polymer was recovered. Analysis of the polymerby GPC indicated Mw and Mn to be 528000 and 40000 respectively.

Example 39.2

[0343] A 1 liter reactor was heated under flowing nitrogen for 1 hour at80° C. before being cooled to 30° C. Isobutane (500 ml) followed bytriisobutyl aluminium (3 ml of 1M in hexanes) was added to the reactor.The reactor was heated to 78° C. and the pressure increased to 13.4 bar.Ethylene was added to give 21.2 bar total pressure. The catalyst ofExample 37.1 (0.124 g, slurried in hexane) was injected into thereactor. The ethylene pressure was estimated to be approximately 8.1 barduring the polymerisation and the temperature adjusted to 80° C.Polymerisation was allowed to continue for 60 minutes. 47 g of polymerwas recovered. Analysis of the polymer by GPC indicated Mw and Mn to be376000 and 40000 respectively.

Example 39.3

[0344] A 1 liter reactor was heated under flowing nitrogen for 1 hour at80° C. before being cooled to 30° C. Triisobutyl aluminium (3 ml of 1Min hexanes) was added to the reactor followed by 500 ml of isobutane.The reactor was heated to 78° C. and the pressure increased to 13.0 bar.Ethylene was added to give 26.0 bar total pressure. The catalyst ofExample 37.1 (0.0966 g, slurried in hexane and 0.25 ml of NNdimethylaniline for 20 minutes) was injected into the reactor. Thepressure in the reactor was allowed to fall to 22.5 bar to reduce theactivity of the catalyst. The ethylene pressure in the reactor duringthe majority of the polymerisation was estimated to be 9.0 bar.Polymerisation was allowed to continue for 60 minutes. 88 g of polymerwas recovered. Analysis of the polymer by GPC indicated Mw and Mn to be430000 and 35000 respectively.

Example 39.4

[0345] A 1 liter reactor was heated under flowing nitrogen for 1 hour at80° C. before being cooled to 30° C. Triisobutyl aluminium (3 ml of 1Min hexanes) was added to the reactor followed by 500 ml of isobutane.The reactor was heated to 78° C. and the pressure increased to 12.7 bar.Ethylene was added to give 14.7 bar total pressure. The catalyst ofExample 37.1(0.104 g, slurried in hexane) was injected into the reactor.The ethylene pressure during the polymerisation was estimated to beapproximately 2.2 bar. Polymerisation was allowed to continue for 60minutes. 4.8 g of polymer was recovered. Analysis of the polymer by GPCindicated Mw and Mn to be 340000 and 36000 respectively.

Example 40

[0346] 40.1 Preparation of 2.6-diacetylpyridinebis(triphenylmethylimine)

[0347] To a solution of 2,6-diacetylpyridine (0.34 g; 2.1 mmol) intoluene (75 ml) was added triphenylmethylamine (1.20 g; 4.6 mmol.).After the addition of toluene sulphonic acid-monohydrate (0.05 g) thesolution was refluxed overnight through a Dean-Stark apparatus. Uponcooling to room temperature the volatile components of the reactionmixture were removed in vacuo and the product crystallised frommethanol. The product was filtered, washed with cold methanol and driedin a vacuum oven (30° C.) overnight. The yield was 1.02 g (33%).

[0348] 40.2 Preparation2.6-diacetylpyridinebis(triphenylmethylimine)FeBr₂

[0349] FeBr₂ (0.182 g; 0.84 mmol) was dissolved in hot n-butanol (30 ml)at 80° C. and solid 2,6-diacetylpyridinebis(triphenylmethylamine) (0.60g; 0.93 mmol) was added in a number of portions. The reaction mixtureturned purple. After stirring at 80° C. for 60 minutes the reaction wasallowed to cool down to room temperature. Stirring was continued for 25hours. The volatile components of the solution were removed underreduced pressure and the resultant purple solid washed with pentane(2×20 cm³) and dried in vacuo. The yield was 0.362 g (64% oftheoretical).

[0350] 40.3 Polymerisation Test

[0351] A polymerisation test was carried out using the followingprocedure. The 2,6-diacetylpyridinebis(triphenylmethylamine)FeBr₂catalyst (0.008 millimoles) was added to a Schlenk tube, suspended intoluene (15 ml) and methylalumoxane cocatalyst (“MAO”) was added toprovide a mole ratio of MAO: Fe complex of 1000:1. The tube was purgedwith ethylene and the contents were mechanically stirred and maintainedunder 1 bar ethylene for the duration of the polymerisation. Afterninety minutes the polymerisation was terminated by the addition ofaqueous hydrogen chloride. The produced solid polyethylene was filteredoff, washed with methanol and dried in a vacuum oven at 50° C. The yieldof polyethylene was 0.185 g. This corresponds to a catalyst activity of16 g mmol⁻¹h⁻¹bar⁻¹. No attempt was made to measure the quantity of anysoluble polymer that may have been produced in this Example.

1. A polymerisation catalyst comprising (1) a nitrogen-containingtransition metal compound having the following Formula B, and (2) anactivating quantity of an activator compound selected fromorganoaluminium compounds and hydrocarbylboron compounds,

 wherein M[T] is Fe[II], Fe[III], Co[I], Co[II], Co[III], Ru[II],Ru[III], Ru[IV], Mn[I], Mn[II], Mn[III] or Mn[IV]; X represents an atomor group covalently or ionically bonded to the transition metal M; T isthe oxidation state of the transition metal M and b is the valency ofthe atom or group X; R¹, R², R³, R⁴, and R⁶ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl and such that (1): when M is Fe, Co or Ru, R⁵ and R⁷ are independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; and when any two ormore of R¹-R⁷ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents, or such that (2): when M is Fe, Co, Mn or Ru, then R⁵ is represented by the group “P” andR⁷ is represented by the group “Q” as follows:

 wherein R¹⁹ to R²⁸ are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and R¹⁹ to R²⁸are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents; with the proviso that at least one ofR¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl when neither of thering systems P and Q forms part of a polyaromatic fused-ring system, orsuch that (3)  when M is Fe, Co, Mn or Ru, then R⁵ is a group having theformula —NR²⁹R³⁰ and R⁷ is a group having the formula —NR³¹R³², whereinR²⁹ to R³² are independently selected from hydrogen, halogen,hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; when any two or more of R¹ to R⁴, R⁶ and R²⁹ to R³²are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl, said two or more can be linked to formone or more cyclic substituents.
 2. A catalyst as claimed in claim 1wherein, in Formula B, M[T] is Fe[II], Fe[III], Ru[II], Ru[III] orRu[IV]; X represents an atom or group covalently or ionically bonded tothe transition metal M; T is the oxidation state of the transition metalM and b is the valency of the atom or group X; R¹, R², R³, R⁴, R⁵, R⁶and R⁷ are independently selected from hydrogen, halogen, hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl; and when any two or more of R¹-R⁷ are hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl, said two or more can be linked to form one or morecyclic substituents.
 3. A catalyst as claimed in claim 1 wherein theFormula B compound has the following Formula Z

wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II],Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atom orgroup covalently or ionically bonded to the transition metal M; T is theoxidation state of the transition metal M and b is the valency of theatom or group X; R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents; with the proviso thatat least one of R¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl whenneither of the ring systems P and Q forms part of a polyaromaticfused-ring system.
 4. A catalyst as claimed in claim 3 wherein neitherof the ring systems P and Q forms part of a polyaromatic ring system,and wherein at least one of R¹⁹ and R²⁰, and at least one of R²¹ and R²²is selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbylor substituted heterohydrocarbyl.
 5. A catalyst as claimed in claim 3wherein neither of the ring systems P and Q forms part of a polyaromaticfused-ring system and wherein each of R¹⁹, R²⁰ R²¹ and R²² is selectedfrom hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl.
 6. A catalyst as claimed in claim 1wherein the Formula B compound has the following Formula T

and wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II],Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atom orgroup covalently or ionically bonded to the transition metal M; T is theoxidation state of the transition metal M and b is the valency of theatom or group X; R¹ to R⁴, R⁶ and R²⁹ to R³² are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R²⁹ to R³² are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents.
 7. A catalyst asclaimed in claim 1 wherein the Formula B compound has the followingFormula W

wherein X represents an atom or group covalently or ionically bonded tothe cobalt atom; T is the oxidation state of the cobalt atom and can beCo[I], Co[II], Co[III], and b is the valency of the atom or group X; R¹,R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from hydrogen,halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl orsubstituted heterohydrocarbyl; and when any two or more of R¹-R⁷ arehydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl, said two or more can be linked to form one or morecyclic substituents.
 8. A catalyst as claimed in any one of thepreceding claims wherein X is selected from halide, sulphate, nitrate,thiolate, thiocarboxylate, BF₄ ⁻, PF₆ ⁻, hydride, hydrocarbyloxide,carboxylate, hydrocarbyl, substituted hydrocarbyl and heterohydrocarbyl.9. A catalyst as claimed in any one of claims 1 to 7 wherein X isselected from chloride, bromide, methyl, ethyl, propyl, butyl, octyl,decyl, phenyl, benzyl, methoxide, ethoxide, isopropoxide, tosylate,triflate, formate, acetate, phenoxide and benzoate.
 10. A catalyst asclaimed in any one of the preceding claims wherein the organoaluminiumcompound is a trialkylaluminium compound.
 11. A catalyst as claimed inany one of the preceding claims wherein the organoaluminium compound isan alumoxane.
 12. A catalyst as claimed in any one of claims 1 to 9wherein the hydrocarbylboron compound is selected fromdimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate,triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate,sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate,H(OEt₂)[(bis-3,5-trifluoromethyl)phenyl]borate,trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.13. A catalyst as claimed in any one of the preceding claimscharacterised in that the catalyst is supported on a support material.14. A catalyst as claimed in claim 13 wherein the support material issilica, alumina, or zirconia, or a polymer or prepolymer.
 15. A catalystas claimed in claim 13 or 14 wherein formation of the supported catalystis achieved by treating the defined nitrogen-containing transition metalcompound with alumoxane in a volatile hydrocarbon inert diluent,slurrying a particulate support material with the product andevaporating the volatile diluent.
 16. A catalyst as claimed in claim 15in the form of a free-flowing powder.
 17. A catalyst system comprisingthe catalyst claimed in any one of the preceding claims and furthercomprising (3) a neutral Lewis base.
 18. A catalyst system comprisingthe catalyst claimed in claim 17 wherein the neutral Lewis base is atertiary amine or an aromatic ester.
 19. A process for thepolymerisation or copolymerisation of 1-olefins comprising contactingthe monomeric olefin under polymerisation conditions with thepolymerisation catalyst claimed in any one of the preceding claims. 20 Aprocess a claimed in claim 19 wherein the monomer is ethylene,propylene, butene, hexene, methyl methacrylate, methyl acrylate, butylacrylate, acrylonitrile, vinyl acetate or styrene.
 21. A process asclaimed in claim 19 wherein the process is for the homopolymerisation ofethylene or propylene.
 22. A process as claimed in claim 19 whereinethylene is copolymerised with another 1-olefin selected from propylene,1-butene, 1-hexene, 4-methylpentene-1, and octene 23 A process asclaimed in any one of claims 19 to 22 wherein hydrogen gas is added tothe polymerisation to control the average molecular weight of theproduced polymer.
 24. A process as claimed in any one of claims 19 to 23wherein the polymerisation temperature is in the range 50 to 120° C. andthe pressure is in the range 10 to 50 bar.
 25. A process as claimed inclaim 19 wherein the polymerisation conditions are solution phase,slurry phase or gas phase.
 26. A process as claimed in claim 19 whereinthe polymerisation is conducted under gas phase fluidised bedconditions.
 27. A process as claimed in claim 26 wherein volatile liquidis fed to the fluidised bed under conditions such that the liquidevaporates in the bed thereby absorbing additional heat ofpolymerisation from the bed.
 28. A process as claimed in claim 27wherein the volatile liquid is condensed out in a heat exchanger.
 29. Aprocess as claimed in claim 28 wherein said volatile liquid is separatedfrom the recycle gas.
 30. A process as claimed in claim 29 wherein saidvolatile liquid is sprayed into the bed.
 31. A process as claimed inclaim 28 wherein said volatile liquid is recycled to the bed withrecycle gas.
 32. A process as claimed in claim 26 wherein hydrogen gasis added to the polymerisation to control the average molecular weightof the produced polymer.
 33. A process as claimed in claim 26 whereinthe polymerisation temperature is in the range 50 to 120° C. and thepressure is in the range 10 to 50 bar.
 34. Polyethylene powdercontaining a catalyst comprising a nitrogen-containing Fe complexwherein the Fe concentration is 1.03 to 0.11 parts by weight of Fe permillion parts by weight of polyethylene.
 35. Polyethylene powder asclaimed in claim 34 wherein the catalyst is the catalyst claimed in anyone of claims 1 to
 16. 36. Polyethylene powder as claimed in claim 34wherein the complex is obtainable from a nitrogen-containing transitionmetal compound of Formula B as defined in claim
 1. 37. Anitrogen-containing transition metal compound comprising the skeletalunit depicted in Formula B

wherein M is Fe[II], Fe[III], Ru[II], Ru[III] or Ru[IV]; X represents anatom or group covalently or ionically bonded to the transition metal M;T is the oxidation state of the transition metal M and b is the valencyof the atom or group X; R¹, R², R³, R⁴ and R⁶ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; R⁵ and R⁷ areindependently selected from hydrogen, halogen, hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl.
 38. Anitrogen-containing transition metal compound as claimed in claim 37wherein R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are independently selected fromhydrogen and C₁ to C₈ hydrocarbyl.
 39. A nitrogen-containing transitionmetal compound as claimed in claim 37 or 38 wherein R¹ to R⁴, R⁶ and R¹⁹to R²⁸ are independently selected from methyl, ethyl, n-propyl, n-butyl,n-hexyl, and n-octyl.
 40. A nitrogen-containing transition metalcompound as claimed in claim 37, 38 or 39 wherein R⁵ and R⁷ areindependently selected from phenyl, 1-naphthyl, 2-naphthyl,2-methylphenyl, 2-ethylphenyl, 2,6-diisopropylphenyl,2,3-diisopropylphenyl, 2,4-diisopropylphenyl, 2,6-di-n-butylphenyl,2,6-dimethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,2-t-butylphenyl, 2,6-diphenylphenyl, 2,4,6-trimethylphenyl,2,6-trifluoromethylphenyl. 4-bromo-2,6-dimethylphenyl, 3,5dichloro2,6-diethylphenyl, and 2,6,bis(2,6-dimethylphenyl)phenyl,cyclohexyl and pyridinyl.
 41. The complex2,6-diacetylpyridinebis(2,4,6-trimethylanil)FeCl₂.
 42. Anitrogen-containing transition metal compound comprising the skeletalunit depicted in Formula Z:

wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II],Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atom orgroup covalently or ionically bonded to the transition metal M; T is theoxidation state of the transition metal M and b is the valency of theatom or group X; R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents, with the proviso thatat least one of R¹⁹, R²⁰, R²¹ and R²² is hydrocarbyl, substitutedhydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl whenneither of the ring systems P and Q forms part of a polyaromaticfused-ring system.
 43. A nitrogen-containing transition metal compoundas claimed in claim 42 wherein R¹ to R⁴, R⁶ and R¹⁹ to R²⁸ areindependently selected from hydrogen and C₁ to C₈ hydrocarbyl, forexample, methyl, ethyl, n-propyl, n-butyl, n-hexyl, and n-octyl.
 44. Anitrogen-containing transition metal compound as claimed in claim 42wherein and at least one of R¹⁹ and R²⁰, and at least one of R²¹ andR²², is selected from hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl and wherein neitherof the ring systems P and Q forms part of a polyaromatic ring system.45. A nitrogen-containing transition metal compound as claimed in claim42 wherein R¹⁹, R²⁰, R²¹ and R²² are each selected from hydrocarbyl,substituted hydrocarbyl, heterohydrocarbyl or substitutedheterohydrocarbyl.
 46. A nitrogen-containing transition metal compoundcomprising the skeletal unit depicted in Formula T:

wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[II], Mn[I], Mn[II],Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atom orgroup covalently or ionically bonded to the transition metal M; T is theoxidation state of the transition metal M and b is the valency of theatom or group X; R¹ to R⁴, R⁶ and R²⁹ to R³² are independently selectedfrom hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R²⁹ to R³² are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents.
 47. A compound havingthe general Formula E as follows:

wherein R¹⁰, R¹¹, R¹² and R¹³ are independently selected from C₁ to C₂₀hydrocarbon groups; and R¹⁴, R¹⁵ and all the remaining ring substituentson the pyridine and benzene rings depicted in Formula E areindependently selected from hydrogen and C₁ to C₂₀ hydrocarbon groups.48. A compound having the general Formula P as follows:

wherein R¹ to R⁴, R⁶ and R²⁹ to R³² are independently selected fromhydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl; when any two or moreof R¹ to R⁴, R⁶ and R²⁹ to R³² are hydrocarbyl, substituted hydrocarbyl,heterohydrocarbyl or substituted heterohydrocarbyl, said two or more canbe linked to form one or more cyclic substituents.
 49. Use of a compoundas defined in any one of claims 37 to 48 as a catalyst for thepolymerisation or co-polymerisation of 1-olefins.